Rozprawy doktorskie na temat „Weakly Bound Molecules/Complexes”

High resolution microwave spectra for the transition metal compounds cobalt tri-carbonyl nitrosyl (Co(CO)₃NO), cyclopentadienyl cobalt di-carbonyl (CpCo(CO)₂), and cyclopentadienyl manganese tri-carbonyl (CpMn(CO)₃) were obtained for the first time using pulsed beam Fourier transform spectroscopy. An oblate symmetric top spectrum was measured for Co(CO)₃NO and the first gas phase value of the cobalt nuclear quadrupole coupling parameter was obtained. The asymmetric top hindered rotor spectrum for CpCo(CO)₂ was measured and a barrier to internal rotation was estimated from the spectrum. Analysis of the prolate symmetric top hyperfine spectrum of CpMn(CO)₃ yielded the first gas phase measurement of the rotational constant and the Mn nuclear quadrupole coupling. High resolution microwave spectra for the iron containing transition metal complexes cyclobutadiene iron tri-carbonyl (CbFe(CO)₃), cyclohexadiene iron tri-carbonyl (C-hexFe(CO)₃) were obtained and a Kraitchman analysis of the isotopic substitution data for the butadiene iron tri-carbonyl (BuFe(CO)₃) is also discussed. Structural parameters for the HCCH-CO were obtained from the various isotopomers for this complex. An analysis of the distortion parameter D(J) yielded an estimation of the binding energy for this weakly bound complex. Analysis of spectra for nitrosyl chloride (NOCl) and chlorine tri-fluoride (ClF₃) yielded the first high resolution low J data sets for these molecules. The quadrupole coupling data are interpreted using the Townes-Dailey model for quadrupole coupling and an improved ground state structure for ClF₃ was obtained. Microwave spectra reported here were obtained using a pulsed beam Fourier transform microwave spectrometer constructed at the University of Arizona. The design is similar to original Flygare-Balle apparatus with many modifications for improving signal sensitivity and data acquisition.

My research interests during my doctoral years have been focused on high resolution rotational studies of molecules and weakly bound molecular complexes. Information on the molecular structure, internal motions and intermolecular interactions that can be obtained by applying suitable theoretical models to the analysis of these unusually complex spectra allows the determination and understanding of the driving forces involved in formation of the molecular complex. In this way, many types of non-covalent interactions have been characterized, from pure van der Waals interactions in complexes of rare gases to moderate-strength and weak hydrogen bonds (HBs) and to the most recent halogen bonds, pnicogen4 or chalcogen bonds. In this thesis, we first introduce the theory of rotational spectroscopy, including that of the asymmetrical rotor, the effects of centrifugal distortion, nuclear quadrupole coupling effects end those of internal motions In the second part, we introduce the experimental apparatuses that were used and related theoretical knowledge. In the third part, chloropentafluorobenzene (C6F5Cl) and bromopentafluorobenzene (C6F5Br) are chosen as case studies to investigate the effect of perfluorination on the molecular structure and electronic properties.In the fourth and fifth parts, we discuss the 1:1 complexes of acrolein-methanol and acrolein-ethanol. In chapter six to eight I report the results on the microwave detection and analysis of the 1:1 complexes of dimethyl sulfoxide (DMSO) with water, methanol and ethanol, respectively, in the gas phase.

This thesis is concerned with the computational simulation of weakly bound molecules. Two general methods of producing potential energy surfaces, Neural Networks and Gaussian processes, are described and evaluated. The Neural Network method is used to generate potential functions for HF-HCI, H₂-HF and H₂-HCI from good quality ab initio data. These surfaces are used by the diffusion Monte Carlo algorithm to solve the vibrational Schrödinger equation for the ground state of the above clusters. In addition, the DMC method is used in a size selective study of the N⁺₂-He_n system. Good agreement is obtained with previous theoretical calculations and with the small amount of experimental data available and it is hoped that the predictions made will aid future studies of these clusters. The combined ab initio-Neural-DMC approach is shown to be an efficient method of studying weakly bound molecules and as such will prove to be a useful step towards understanding the structure and bonding of these systems.

High resolution rotational spectra were obtained for a several weakly-bound complexes (WBC) and one transition metal organometallic molecule, cyclopentadienylnickel nitrosyl (CpNiNO), using pulsed-beam, Fourier transform microwave spectroscopy. The weakly-bound complexes included the two structural isomers of N₂O-HF, the planar bent asymmetric N₂O-HCN complex, the planar bent asymmetric N₂O-HCl complex, and the "stacked" H₂S-SO₂, and H₂S-CO₂ complexes. In all of the cases with the exclusion of the CpNiNO molecule, additional isotopic measurements were obtained to aid in the spectral and structural analyses of the weakly-bound complexes. Analysis of rotational spectra was used to determine several spectroscopic constants. For each WBC and CpNiNO rotational constants and some quartic distortion parameters were determined. In the experimental studies performed on N₂O-HCN and N₂O-HCl additional quadrupole coupling components were determined from the data analysis. Structural analyses were performed on all of the WBC's. Isotopic Kraitchman analysis was used as a comparative guideline in helping to select the lowest energy vibrationally-averaged structure. High resolution (0.005 cm⁻¹) infrared spectra for CpNiNO were obtained with the Fourier transform spectrometer in the Kitt Peak McMath Solar Telescope. Absorption spectra were measured in the 1750-1880 cm⁻¹ and 2500-3700⁻¹ regions. A program written by Dr. Clive Jarman, a postdoc in Dr. Peter Bernath's laboratory, was used to perform Loomis-Wood analysis of 2 significant patterns in the 2500-3700 cm⁻¹ range. The series determined from the Loomis-Wood analysis are given in the dissertation.

Mon projet de thèse a eu pour objectif la construction d'un dispositif expérimental visant à étudier, à très basse température, un mélange de gaz dégénéré composé de deux espèces fermioniques: 6Li et 40K. Une description détaillée du montage de sa mise en place ainsi qu'une caractérisation du dispositif sont présentées. Nous avons réalisé un piège magnéto-optique à deux espèces avec un très grand nombre d'atomes, et un transport magnétique sur une grande distance. Les premières expériences avec le mélange atomique ont permis la première création de molécules hétéronucléaires excitées 6Li40K* par photoassociation. Nous avons enregistré et assigné des spectres de photoassociation pour les états les plus faiblement liés de sept potentiels moléculaires et nous en avons déduit la forme des potentiels à longues distances. Nos résultats ouvrent la voie vers la formation de molécules bosoniques 6Li40K ultra-froides dans leur état fondamental, caractérisé par un grand moment dipolaire électrique permanent. Sur le plan théorique, nous avons développé une nouvelle méthode pour la manipulation des particules quantiques, qui pourrait être appliquée aux molécules 6Li40K. Cette méthode consiste à piéger les particules dans un potentiel oscillant rapidement et induire un changement instantané de phase du potentiel (un saut de phase). Nous montrons que le mouvement moyen des particules peut ainsi être manipulé de manière contrôlée. La méthode proposée a trouvé une première application pour les condensats de Bose-Einstein piégés à l'aide d'un piège magnétique du type "TOP".

The work presented in this thesis applies laser spectroscopy, matrix isolation and ab initio calculations to the study of free radicals and weakly bound species. The C - X region of BaOH has been re-investigated in the gas phase at higher resolution than by previous workers. A new assignment of the recorded spectra is tentatively proposed based on the higher resolution achieved. The spectrum appears to be heavily perturbed, which seriously complicates the spectral assignment. A new basis set extrapolation procedure has been developed for ab initio calculations on van der Waals complexes. The procedure developed, a modification of the Truhlar extrapolation, employs calculations using modest sized basis sets. This has been tested on 15 van der Waals species with well known equilibrium dissociation energies and bond distances. The modified Truhlar extrapolation procedure is found to be generally of comparative accuracy to CCSD(T)/aug-cc-pV5Z calculations but at much reduced computational cost. The modified Truhlar extrapolation has been applied for the first time to HRgF molecules, where Rg is Ar, Ne and He. The potential energy surfaces generated for HHeF and HNeF represent the most accurate ab initio calculations to date on these species. The HArF calculations are of comparable accuracy to aug-cc-pV5Z calculations by other workers. Vibrational frequencies have also been calculated for all three molecules. The modified Truhlar extrapolation procedure has been applied for the first time to RgC2 clusters, where Rg is Ar, Ne and He. The potential energy surfaces generated. Rovibrational frequencies have been calculated for all three clusters. These lead to the conclusion that both ArC2 and NeC2 are spectroscopically observable, although this would be challenging. Matrix isolation apparatus recently built for recording LIF spectra of trapped reactive intermediates has been tested, improved and evaluated. Vibrationally-resolved LIF spectra of benzene have been recorded. A metal containing free radical, CaCl has been trapped and observed using the apparatus.

The first part of this dissertation covers the microwave spectroscopy of the weakly bound complexes HI-HF, H₂S-SO₂, Ar-H₂S, and N₂O-HF. These molecules were investigated using a Flygare-Balle type pulsed-beam Fabry-Perot Fourier-transform microwave spectrometer. The spectrometer and its construction are described. The HI-HF complex was found to be hydrogen bonded through the hydrogen of the HF. The hydrogen bond length was found to be 2.720A with a structure such that the monomer bonds form an acute angle of 70°. For H₂S-SO₂ a structure with a S-S distance of 3.67A and H-O distances of 3.1A was obtained. It was established that the hydrogens of H₂S are equivalent is this species. A new set of transitions for Ar-HDS were observed indicating that the hydrogens in this molecule are not equivalent. Several new transitions were also observed for Ar-H₂³⁴S, Ar-H₂S and Ar-D₂S. New insight into the structure of the Ar-H₂S molecule was obtained. Several new transitions for the bent isomer of N₂O-HF were measured and a fit of the ground state constants for this species was performed including quartic distortion constants. The resulting fit improves calculated line centers by two orders of magnitude over previous results. The second part of this dissertation covers the infrared spectroscopy of the ν₆ and ν₈ bands of formic acid. Fourier transform data for these bands were obtained at 0.01 cm⁻¹ resolution using the spectrometer at the Kitt Peak National solar observatory. Diode laser data at 0.001 cm⁻¹ was obtained for the ν₈ band. A two state a-type Coriolis coupled Hamiltonian was used to perform a global fit on all the available data. A greatly improved set of spectroscopic parameters for these two bands were obtained. This new set of parameters has allowed several previously unassigned far I.R. laser and I.R. laser saturation lines to be assigned. Using these improved constants, it should be possible to predict the frequencies for several formic acid far I.R. laser transitions which are not yet accurately measured.

Weak intermolecular interactions have very strong impact on the structures and properties of life giving molecules like H2O, DNA, RNA etc. These interactions are responsible for many biological phenomena. The directional preference of some of these interactions is used for designing different synthetic approaches in the supramolecular chemistry. The work reported in this Thesis comprises of investigations of weak intermolecular interactions in gas phase using home-built Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer as an experimental tool and ab-initio and Atoms in Molecules (AIM) theory as theoretical tools. The spectrometer which is coupled with a pulsed nozzle is used to record pure rotational spectra of the molecular clusters in a jet cooled molecular beam. In the molecular beam molecules/complexes are free from interactions with other molecules/complexes and thus, spectroscopy in the molecular beams provides information about the 'isolated' molecule/complex under investigation. The rotational spectra of the molecules/complexes in the molecular beam provide their geometry in the ground vibrational states. These experimental geometries can be used to test the performance and accuracy of theoretical models like ab-initio theory, when applied to the weakly bound complexes. Further the AIM theory can be used to gain insights into the nature and strength of the intermolecular interactions present in the system under investigation. Chapter I of this Thesis gives a brief introduction of intermolecular interactions. Other than hydrogen bonding, which is considered as the most important intermolecular interaction, many other intermolecular interactions involving different atoms have been observed in past few decades. The chapter summarizes all these interactions. The chapter also gives a brief introduction to the experimental and theoretical methods used to probe these interactions. In Chapter II, the experimental and theoretical methods used in this work are summarized. Details of our home-built PN-FTMW spectrometer are given in this chapter. The chapter also discusses briefly the theoretical methods like ab-initio, AIM and Natural bond orbital (NBO) analysis. We have made few changes in the mode of control of one of our delay generators which have also been described. Chapter III and Chapter V of this Thesis are dedicated to the propargyl alcohol complexes. Propargyl alcohol (PA) is a molecule of astrophysical interest. It is also important in combustion chemistry since propargyl radical is considered as the precursor in soot formation. Moreover, PA is a multifunctional molecule, having a hydroxyl (-OH) and an acetylenic (-C≡C-H) group. Both of the groups can individually act as hydrogen bond acceptor as well as donor and thus PA provides an exciting possibility of studying many different types of weak interactions. Due to internal motion of -OH group, PA monomer can exist in gauche as well as trans form. However, rotational spectra of PA-monomer show the presence of only gauche conformer. In Chapter III, rotational spectra of Ar•••PA complex are discussed. The pure rotational spectra of the parent Ar•••PA complex and its two deuterated isotopologues, Ar•••PA-D (OD species) and Ar•••PA-D (CD species), could be observed and fitted within experimental uncertainty. The structural fitting confirmed a structure in which PA is present as gauche conformer and argon interacts with both the O-H group and the acetylenic group leading to Ar•••H-O and Ar•••π interactions respectively. Presence of these interactions was further confirmed by AIM theoretical analysis. In all the three isotopologues c-type rotational transitions showed significant splitting. Splitting patterns in the three isotopologues suggest that it originates mainly due to the large amplitude motion of the hydroxyl group and the motion is weakly coupled with the carbon chain bending motion. No evidence for the complex with trans conformer of PA was found. Although, we could not observe Ar•••trans-PA complex experimentally, we decided to perform ab-initio and AIM theoretical calculations on this complex as well. AIM calculations suggested the presence of Ar•••H-O and a unique Ar•••C interaction in this complex which was later found to be present in the Ar•••methanol complex as well. This prompted us to explore different possible interactions in methanol, other than the well known O-H•••O hydrogen bonding interactions, and eventually led us to an interesting interaction which we termed as carbon bond. Chapter IV discusses carbon bonding interaction in different complexes. Electrostatic potential (ESP) calculations show that tetrahedral face of methane is electron-rich and thus can act as hydrogen/halogen bond acceptor. This has already been observed in many complexes, e.g. CH4•••H2O/HF/HCl/ClF etc., both experimentally and theoretically. However, substitution of one of the hydrogens of methane with -OH leads to complete reversal of the properties of the CH3 tetrahedral face and this face in methanol is electron-deficient. We found that CH3 face in methanol interacts with electron rich sites of HnY molecules and leads to the formation of complexes stabilized by Y•••C-X interactions. This interaction was also found to be present in the complexes of many different CH3X (X=OH/F/Cl/Br/NO2/NF2 etc.) molecules. AIM, NBO and C-X frequency shift analyses suggest that this interaction could be termed as "carbon bond". The carbon bonding interactions could be important in understanding hydrophobic interactions and thus could play an important role in biological phenomena like protein folding. The carbon bonding interaction could also play a significant role in the stabilization of the transition state in SN2 reactions. In Chapter V of this Thesis rotational spectra of propargyl alcohol dimer are discussed. Rotational spectra of the parent dimer and its three deuterated (O-D) isotopologues (two mono-substituted and one bi-substituted) could be recorded and fitted within experimental uncertainty. The fitted rotational constants are close to one of the ab-initio predicted structure. In the dimer also propargyl alcohol exists in the gauche form. Atoms in molecules analysis suggests that the experimentally observed dimer is bound by O-H•••O, O-H•••π and C-H•••π interactions. Chapter VI of the thesis explores the 'electrophore concept'. To observe the rotational spectra of any species and determine its rotational constant by microwave spectroscopy, the species should have a permanent dipole moment. Can we obtain rotational constants of a species having no dipole moment via microwave spectroscopy? Electrophore concept can be used for this purpose. An electrophore is an atom or molecule which could combine with another molecule having no dipole moment thereby forming a complex with a dipole moment, e.g. Argon atom is an electrophore in Ar•••C6H6 complex. The microwave spectra of Ar•••13CC5H6 and Ar•••C6H5D complexes were recorded and fitted. The A rotational constant of these complexes was found to be equal to the C rotational constant of 13CC5H6 and C6H5D molecules respectively and thus we could determine the C rotational constant of microwave 'inactive' 13CC5H6. This concept could be used to obtain the rotational spectra of parallel displaced benzene-dimer if it exists. We recently showed that the square pyramidal Fe(CO)5 can act as hydrogen bond acceptor. Appendix I summarizes the extension of this work and discusses interactions of trigonal bipyramidal Fe(CO)5 with HF, HCl, HBr and ClF. Our initial attempts on generating a chirped pulse to be used in a new broadband spectrometer are summarized in Appendix II. Preliminary investigations on the propargyl•••water complex are summarized in Appendix III.

Weak intermolecular interactions have very strong impact on the structures and properties of life giving molecules like H2O, DNA, RNA etc. These interactions are responsible for many biological phenomena. The directional preference of some of these interactions is used for designing different synthetic approaches in the supramolecular chemistry. The work reported in this Thesis comprises of investigations of weak intermolecular interactions in gas phase using home-built Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer as an experimental tool and ab-initio and Atoms in Molecules (AIM) theory as theoretical tools. The spectrometer which is coupled with a pulsed nozzle is used to record pure rotational spectra of the molecular clusters in a jet cooled molecular beam. In the molecular beam molecules/complexes are free from interactions with other molecules/complexes and thus, spectroscopy in the molecular beams provides information about the 'isolated' molecule/complex under investigation. The rotational spectra of the molecules/complexes in the molecular beam provide their geometry in the ground vibrational states. These experimental geometries can be used to test the performance and accuracy of theoretical models like ab-initio theory, when applied to the weakly bound complexes. Further the AIM theory can be used to gain insights into the nature and strength of the intermolecular interactions present in the system under investigation. Chapter I of this Thesis gives a brief introduction of intermolecular interactions. Other than hydrogen bonding, which is considered as the most important intermolecular interaction, many other intermolecular interactions involving different atoms have been observed in past few decades. The chapter summarizes all these interactions. The chapter also gives a brief introduction to the experimental and theoretical methods used to probe these interactions. In Chapter II, the experimental and theoretical methods used in this work are summarized. Details of our home-built PN-FTMW spectrometer are given in this chapter. The chapter also discusses briefly the theoretical methods like ab-initio, AIM and Natural bond orbital (NBO) analysis. We have made few changes in the mode of control of one of our delay generators which have also been described. Chapter III and Chapter V of this Thesis are dedicated to the propargyl alcohol complexes. Propargyl alcohol (PA) is a molecule of astrophysical interest. It is also important in combustion chemistry since propargyl radical is considered as the precursor in soot formation. Moreover, PA is a multifunctional molecule, having a hydroxyl (-OH) and an acetylenic (-C≡C-H) group. Both of the groups can individually act as hydrogen bond acceptor as well as donor and thus PA provides an exciting possibility of studying many different types of weak interactions. Due to internal motion of -OH group, PA monomer can exist in gauche as well as trans form. However, rotational spectra of PA-monomer show the presence of only gauche conformer. In Chapter III, rotational spectra of Ar•••PA complex are discussed. The pure rotational spectra of the parent Ar•••PA complex and its two deuterated isotopologues, Ar•••PA-D (OD species) and Ar•••PA-D (CD species), could be observed and fitted within experimental uncertainty. The structural fitting confirmed a structure in which PA is present as gauche conformer and argon interacts with both the O-H group and the acetylenic group leading to Ar•••H-O and Ar•••π interactions respectively. Presence of these interactions was further confirmed by AIM theoretical analysis. In all the three isotopologues c-type rotational transitions showed significant splitting. Splitting patterns in the three isotopologues suggest that it originates mainly due to the large amplitude motion of the hydroxyl group and the motion is weakly coupled with the carbon chain bending motion. No evidence for the complex with trans conformer of PA was found. Although, we could not observe Ar•••trans-PA complex experimentally, we decided to perform ab-initio and AIM theoretical calculations on this complex as well. AIM calculations suggested the presence of Ar•••H-O and a unique Ar•••C interaction in this complex which was later found to be present in the Ar•••methanol complex as well. This prompted us to explore different possible interactions in methanol, other than the well known O-H•••O hydrogen bonding interactions, and eventually led us to an interesting interaction which we termed as carbon bond. Chapter IV discusses carbon bonding interaction in different complexes. Electrostatic potential (ESP) calculations show that tetrahedral face of methane is electron-rich and thus can act as hydrogen/halogen bond acceptor. This has already been observed in many complexes, e.g. CH4•••H2O/HF/HCl/ClF etc., both experimentally and theoretically. However, substitution of one of the hydrogens of methane with -OH leads to complete reversal of the properties of the CH3 tetrahedral face and this face in methanol is electron-deficient. We found that CH3 face in methanol interacts with electron rich sites of HnY molecules and leads to the formation of complexes stabilized by Y•••C-X interactions. This interaction was also found to be present in the complexes of many different CH3X (X=OH/F/Cl/Br/NO2/NF2 etc.) molecules. AIM, NBO and C-X frequency shift analyses suggest that this interaction could be termed as "carbon bond". The carbon bonding interactions could be important in understanding hydrophobic interactions and thus could play an important role in biological phenomena like protein folding. The carbon bonding interaction could also play a significant role in the stabilization of the transition state in SN2 reactions. In Chapter V of this Thesis rotational spectra of propargyl alcohol dimer are discussed. Rotational spectra of the parent dimer and its three deuterated (O-D) isotopologues (two mono-substituted and one bi-substituted) could be recorded and fitted within experimental uncertainty. The fitted rotational constants are close to one of the ab-initio predicted structure. In the dimer also propargyl alcohol exists in the gauche form. Atoms in molecules analysis suggests that the experimentally observed dimer is bound by O-H•••O, O-H•••π and C-H•••π interactions. Chapter VI of the thesis explores the 'electrophore concept'. To observe the rotational spectra of any species and determine its rotational constant by microwave spectroscopy, the species should have a permanent dipole moment. Can we obtain rotational constants of a species having no dipole moment via microwave spectroscopy? Electrophore concept can be used for this purpose. An electrophore is an atom or molecule which could combine with another molecule having no dipole moment thereby forming a complex with a dipole moment, e.g. Argon atom is an electrophore in Ar•••C6H6 complex. The microwave spectra of Ar•••13CC5H6 and Ar•••C6H5D complexes were recorded and fitted. The A rotational constant of these complexes was found to be equal to the C rotational constant of 13CC5H6 and C6H5D molecules respectively and thus we could determine the C rotational constant of microwave 'inactive' 13CC5H6. This concept could be used to obtain the rotational spectra of parallel displaced benzene-dimer if it exists. We recently showed that the square pyramidal Fe(CO)5 can act as hydrogen bond acceptor. Appendix I summarizes the extension of this work and discusses interactions of trigonal bipyramidal Fe(CO)5 with HF, HCl, HBr and ClF. Our initial attempts on generating a chirped pulse to be used in a new broadband spectrometer are summarized in Appendix II. Preliminary investigations on the propargyl•••water complex are summarized in Appendix III.

Atoms construct the molecules and molecules construct the material substances (with the exceptions as well, e.g.., metals, where atoms directly construct the material substances). Intermolecular interactions play an important role in most of the branches of sciences, ranging from material sciences to biological sciences. Van der Waals interactions are weak intermolecular interactions while hydrogen bonding varies in strength from weak to strong (1 to 40 kcal/mol). The present work focuses on applying some theoretical methods (ab initio and Atoms in Molecules theory) on these interactions to differentiate them with physically meaningful parameters such as hydrogen bond radii and atoms in molecules theory parameters. 1)Defining and calculating H-bond radii have been done using atoms in molecules theory approach which can explain ruling out the presence or absence of an H-bond in an intermolecular interaction. 2) A blue-shift of 200 cm-1 for a weakly bound complex is unprecedented. Our studies on weakly bound complexes showed the blue-shift of 200 cm-1 for H3C•••CIF and shift has been found to be purely from the mixing of normal modes and not because of an interaction. 3)Methane, a symmetric top molecule can act both as H-bond acceptor and donor. The present work shows that methane is rather a better H-bond acceptor than a donor and all the calculated parameters are in favor of this description. 4) Microwave spectrometer is an ultimate tool (at least at present) for structural characterization of the weakly bound complexes accurately. The rotational spectrum of the weakly bound isotopomer weakly bound complexes accurately. The rotational spectrum of the weakly bound isotopomer 13CC5H6•••Ar, which is a symmetric top and gives only “B” rotational constant. Moreover, the A rotational constant of the complex is the same as the rotational constant for 13CC5H6, which has no dipole moment. C2H2 molecule is an astrophysically important molecule as it is present in asymptotic giant branch and T-type stars (Teff<3000K). Due to its various infrared active vibrational modes, C2H2 is one of the most important sources in cool stars. The production of C2H2 infrared spectroscopic data at high temperature is therefore essential to trace back physical characteristics of these objects and to model the radiative transfer in their envelope. The databases such as “HITRAN”, do not have enough data available for stimulating high temperature spectra. Keeping all these objectives in mind, high temperature emission spectrum of acetylene has been recorded around 3µm region of acetylene.

Atoms construct the molecules and molecules construct the material substances (with the exceptions as well, e.g.., metals, where atoms directly construct the material substances). Intermolecular interactions play an important role in most of the branches of sciences, ranging from material sciences to biological sciences. Van der Waals interactions are weak intermolecular interactions while hydrogen bonding varies in strength from weak to strong (1 to 40 kcal/mol). The present work focuses on applying some theoretical methods (ab initio and Atoms in Molecules theory) on these interactions to differentiate them with physically meaningful parameters such as hydrogen bond radii and atoms in molecules theory parameters. 1)Defining and calculating H-bond radii have been done using atoms in molecules theory approach which can explain ruling out the presence or absence of an H-bond in an intermolecular interaction. 2) A blue-shift of 200 cm-1 for a weakly bound complex is unprecedented. Our studies on weakly bound complexes showed the blue-shift of 200 cm-1 for H3C•••CIF and shift has been found to be purely from the mixing of normal modes and not because of an interaction. 3)Methane, a symmetric top molecule can act both as H-bond acceptor and donor. The present work shows that methane is rather a better H-bond acceptor than a donor and all the calculated parameters are in favor of this description. 4) Microwave spectrometer is an ultimate tool (at least at present) for structural characterization of the weakly bound complexes accurately. The rotational spectrum of the weakly bound isotopomer weakly bound complexes accurately. The rotational spectrum of the weakly bound isotopomer 13CC5H6•••Ar, which is a symmetric top and gives only “B” rotational constant. Moreover, the A rotational constant of the complex is the same as the rotational constant for 13CC5H6, which has no dipole moment. C2H2 molecule is an astrophysically important molecule as it is present in asymptotic giant branch and T-type stars (Teff<3000K). Due to its various infrared active vibrational modes, C2H2 is one of the most important sources in cool stars. The production of C2H2 infrared spectroscopic data at high temperature is therefore essential to trace back physical characteristics of these objects and to model the radiative transfer in their envelope. The databases such as “HITRAN”, do not have enough data available for stimulating high temperature spectra. Keeping all these objectives in mind, high temperature emission spectrum of acetylene has been recorded around 3µm region of acetylene.

Intermolecular interactions appear to be well understood in a broad sense today; at a deeper molecular level, it is still evolving. Spectroscopy in this isolated state proved to be a first step toward understanding the intermolecular interaction at the molecular level. Microwave spectroscopy offers precise structural information on the near-equilibrium geometry of small dimers and trimers in isolation. Computational studies like the Atoms in Molecules (AIM), non-covalent index plots (NCI), and natural bond orbital analysis (NBO) are used to augment rotational spectroscopic investigations. The Ka = 1 transitions of H2S dimer and several isotopomers were observed in a pulsed nozzle Fourier transform microwave spectrometer. These transitions give unequivocal proof that, at ultra-low temperatures, hydrogen sulfide forms S-H⸳⸳⸳S hydrogen-bonded dimer in the same way as water does, even though ice and solid H2S seem substantially different in bulk. Also, using the AIM theory, we have shown that H2S dimer satisfies the necessary and sufficient criterion proposed by Koch and Popelier to be hydrogen-bonded. Although we recently highlight the arbitrariness in relying on some computational tools to characterize a bond. The weakly bound trimer between two hydrogen sulfide molecules and one water molecule, (H2S)2H2O, was identified from its rotational spectrum. The break with axial molecular symmetry allowed us to investigate (H2S)2H2O at a level of structural detail that has not yet been possible for (H2O)3 and (H2S)3 with rotational spectroscopy owing to their zero-dipole moment. Analysis of experimental results reveals that the three monomers are bound in a triangular arrangement through S-H⸳⸳⸳S, O-H⸳⸳⸳S, and S-H⸳⸳⸳O hydrogen bonds with a fair amount of co-operativity. High-resolution spectroscopic data may be used to validate the correctness of a model intermolecular potential energy hyper-surface. In this regard, we have measured the donor-acceptor interchange tunnelling splitting in the ground vibrational state of Ar-(H2O)2. In the previous investigations, the donor-acceptor tunnelling splitting in fully deuterated species, Ar-(D2O)2, was measured to be 106 MHz. However, it could not be measured for the Ar-(H2O)2,as the splitting was expected to be several GHz. With the help of a fourfold periodic potential, we have accurately predicted the fingerprints of donor-acceptor interchange tunnelling transitions and measured the splitting of 4257.41(4) MHz in Ar-(H2O)2. Lastly, we have looked beyond hydrogen bonding and explored other intermolecular bonding across the Periodic Table. The slopes of the binding energy versus electron density at the bond critical point were derived for each main group element. Our results show that intermolecular bonding can be classified into two types: intermolecular bonding (IMB) with a shared shell molecule (IMB-S) and intermolecular bonding (IMB) with a closed shell molecule (IMB-C). The IMB-S includes hydrogen, halogen, chalcogen, pnictogen, tetrel (excluding carbon bonds), and boron bonds (but not triel bonds). IMB-C contains lithium, sodium, beryllium, magnesium, triel (excluding boron bonds) and carbon bonds. The binding energy versus electron density plot of the IMB-S class generally has a low slope, whereas the IMB-C type has a high slope. Carbon bonds are distinct from the other members of the group. Carbon is a hesitant partner in tetrel bonds due to the absence of lower energy d-orbitals. The electron density between the two atoms is extremely low, and the binding energy grows fast with electron density, resulting in a high slope value for the carbon bond. The slopes for the Li, Na, Be, Mg, Ca-bonds were found out to be comparable, whereas the slope for the hydrogen bond remains standout. Several similarities eventually lead us to propose a common name, ‘Alkalene bond,’ for the intermolecular bonding in alkali and alkaline earth metals.

The weakly bound association products of atmospherically relevant radical species (O₂, OH, NO₂, HO₂ and NO) have been studied theoretically using quantum-chemical methods. The thermodynamic stabilities, which are crucial to determining the probability of formation in Earth's atmosphere, were calculated for the hydrotrioxy radical (HOOO) and peroxynitrous acid (HOONO, an isomer of nitric acid) relative to the radical dissociation products. In the case of HOONO, the experimentally determined values were confirmed. For HOOO, the predicted stability was significantly lower than the experimentally determined value; a conclusion that was supported by later experimental work and indicates that HOOO will not form in significant quantities in Earth's atmosphere. The fundamental and multi-quantum vibrational transitions were also predicted for both the HOONO and HOOO systems. The theoretical work on the HOONO system aided the assignment of experimental spectra and was used to correct equilibrium rotational constants. The HOOO system presented a challenge for the methods used here and work to apply other approaches in describing the vibrational modes is ongoing. Second-order vibrational perturbation theory, combined with a correlated quantum-chemical method and a moderately sized basis set, provides a method for accurately predicting fundamental and low-order multi-quantum transition energies and intensities for many systems (HOOO being an exception). Here coupled cluster theory, at a level which treats one- and two-electron correlation with a correction for three-electron correlation, and atomic natural orbitals basis sets were used in the vibrational calculations. To predict the dissociation energies of weakly bound species with the precision required (due to the small energy differences involved), high-order correlation contributions (a full treatment of three-electron correlation and a correction for four-electron correlation) are included, as is extrapolation to the basis set limit. Other contributions, such as that for the zero-point energy, were also considered. For the HOOO system, one-dimensional potential curves along the dissociation and torsional coordinates were constructed with standard single-reference and equation-of-motion coupled-cluster methods. The latter is better able to describe the nature of a system in the bond-breaking region and the complex electronic structure of a species formed from two radical fragments, one doubly degenerate in the ground state: X²[Pi] OH and X³[Sigma] O₂. A possible barrier to dissociation and the torsional potential for HOOO were investigated.
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In this research the so-called potential morphing method was used to generate reliable interaction potential energy surfaces for weakly bound complexes. The potential morphing method is based on the optimization of modified computed ab initio potential energy surfaces to give predicted spectroscopic data, in agreement with the experimental values. In the standard potential morphing procedure the computed ab initio potential is adjusted by scaling, shifting, and dilating transformations to reproduce the experimental data. In this research, selected systems have been chosen to be studied based on the availability of varied and accurate sets of experimental data. In the present work, accurate interaction potential energy surfaces are obtained for the weakly bound complexes: Ne:HCl, OC:HX (X = F, Cl, Br, I) and HI:CO2. A comprehensive study on the interaction potential of these systems provides fundamental perspectives on the influence of different intermolecular forces. In addition the ground state isotopic isomerization observed in the OC:HI system may suggest a possible structural change of proteins, and other biological macromolecules, in deuterated solvents. In this dissertation, an alternative approach to morphing the potential energy surfaces of non-covalent interactions is also presented. In this approach the morphed potential is generated as a linear combination of ab initio potentials, that are computed at different levels of theory. This new morphing approach is applied to OC:HCl and is found to be of similar accuracy to that of the previous morphing method. In addition, this new method is also extended from four-dimensions to six-dimensions and is applied to the OC:HF system to obtain a vibrationally-complete six-dimensional morphed potential.

Work reported in this thesis mainly comprises of the assignments and analysis of the rotational spectra and structures of three weakly bound complexes: C2H4•••H2S, C6H5CCH•••H2O and C6H5CCH•••H2S. All the data have been collected using a home built Pulsed Nozzle Fourier Transform Microwave Spectrometer. Apart from this, the thesis also deals with a criterion of classifying a weakly bound complex to a ‘hydrogen-bonded’ one. First chapter of the thesis gives a brief intermolecular interactions and molecular clusters of π system. It also briefly touches on the structural determination by rotational spectroscopy and the basic information one can gain from the rotational spectrum. Second chapter of the thesis gives a brief introduction to the experimental and theoretical methodology. It also gives a description of the software used in the FTMW spectrometer which was rebuilt using Labview 7.1. Third chapter of the thesis deals with the rotational spectra and structure of eight isotopologoues of C2H4•••H2S complex. The lines are split into four components for the parent isotopologue due to the presence of large amplitude motion. The smaller splitting is 0.14 MHz and the higher splitting is 1.67 MHz in (B+C)/2 for the parent isotopologue. Spectral splitting pattern of the isotopologues confirmed that smaller splitting is due to the rotation of ethylene about its C-C bond axis along with the contraction of S-H bond whereas the larger motion arises due to the interchange of equivalent hydrogens of H2S in the complex. A detailed spectral analysis and ab initio calculation for this system have been described in chapter III. The fourth chapter of the thesis describes the rotational spectroscopic studies of five isotopologues of C6H5CCH•••H2O complex. Rotational spectra unequivocally confirm the structure of the complex to be a one where H2O is donating one of its hydrogen to the acetylenic π cloud forming a O-H••• π bond whereas the ring ortho C-H bond forms C-H•••O bond with the water oxygen. For theparent isotopomer the lines are split into two components due to the rotation of H2O about its C2 symmetric axis. The fifth chapter of thesis describes the rotational spectroscopic and ab initio studies of five isotopologues of C6H5CCH•••H2S complex. Rotational spectra indicate the structure to be the one where H2S is sitting on the top of the phenyl ring and shifted towards the acetylenic group. The sixth chapter of the thesis describes a criterion for calling a complex to be hydrogen bonded based on the dynamic structure rather than the static structure of the complex. The question asked is if the anisotropy of the interaction is strong enough to hold the ‘hydrogen bond’ when one takes dynamics into account. The proposed criterion is that the zero point energy of the motion which takes the hydrogen away from the acceptor should be much less than the barrier height of the respective motion supporting at least one bound level below the barrier. Ab initio calculations have been done on four model systems Ar2•••H2O, Ar2•••H2S, C2H4••• H2O and C2H4••• H2S to emphasize this criterion.

Work reported in this thesis mainly comprises of the assignments and analysis of the rotational spectra and structures of three weakly bound complexes: C2H4•••H2S, C6H5CCH•••H2O and C6H5CCH•••H2S. All the data have been collected using a home built Pulsed Nozzle Fourier Transform Microwave Spectrometer. Apart from this, the thesis also deals with a criterion of classifying a weakly bound complex to a ‘hydrogen-bonded’ one. First chapter of the thesis gives a brief intermolecular interactions and molecular clusters of π system. It also briefly touches on the structural determination by rotational spectroscopy and the basic information one can gain from the rotational spectrum. Second chapter of the thesis gives a brief introduction to the experimental and theoretical methodology. It also gives a description of the software used in the FTMW spectrometer which was rebuilt using Labview 7.1. Third chapter of the thesis deals with the rotational spectra and structure of eight isotopologoues of C2H4•••H2S complex. The lines are split into four components for the parent isotopologue due to the presence of large amplitude motion. The smaller splitting is 0.14 MHz and the higher splitting is 1.67 MHz in (B+C)/2 for the parent isotopologue. Spectral splitting pattern of the isotopologues confirmed that smaller splitting is due to the rotation of ethylene about its C-C bond axis along with the contraction of S-H bond whereas the larger motion arises due to the interchange of equivalent hydrogens of H2S in the complex. A detailed spectral analysis and ab initio calculation for this system have been described in chapter III. The fourth chapter of the thesis describes the rotational spectroscopic studies of five isotopologues of C6H5CCH•••H2O complex. Rotational spectra unequivocally confirm the structure of the complex to be a one where H2O is donating one of its hydrogen to the acetylenic π cloud forming a O-H••• π bond whereas the ring ortho C-H bond forms C-H•••O bond with the water oxygen. For theparent isotopomer the lines are split into two components due to the rotation of H2O about its C2 symmetric axis. The fifth chapter of thesis describes the rotational spectroscopic and ab initio studies of five isotopologues of C6H5CCH•••H2S complex. Rotational spectra indicate the structure to be the one where H2S is sitting on the top of the phenyl ring and shifted towards the acetylenic group. The sixth chapter of the thesis describes a criterion for calling a complex to be hydrogen bonded based on the dynamic structure rather than the static structure of the complex. The question asked is if the anisotropy of the interaction is strong enough to hold the ‘hydrogen bond’ when one takes dynamics into account. The proposed criterion is that the zero point energy of the motion which takes the hydrogen away from the acceptor should be much less than the barrier height of the respective motion supporting at least one bound level below the barrier. Ab initio calculations have been done on four model systems Ar2•••H2O, Ar2•••H2S, C2H4••• H2O and C2H4••• H2S to emphasize this criterion.

Initiated with the purpose of assigning the Fraunhofer lines in the solar spectrum to atomic transitions in the 18th century, the collaboration between spectroscopists and astrophysicists has remained fruitful, successful and ever fascinating. This collaboration has resulted in the unique detection of over 200 different molecular species in the interstellar medium (ISM). These interstellar molecular species play significant roles in diverse fields such as atmospheric chemistry, astrochemistry, prebiotic chemistry, astrophysics, astronomy, astrobiology, etc, and in our understanding of the solar system ''the world around us''. This Thesis work focuses on understanding of the different aspects of the chemistry of the various classes of these molecular species. Chapter one starts with an historical perspective of what is now regarded as Molecular Astrophysics or Astrochemistry and discusses the interstellar medium and its properties; interstellar molecular species and their importance; molecular spectroscopy as an indispensible tool in interstellar chemistry and the different formation routes of these molecular species. It also discusses hydrogen bonding which is one of the most important of all the intermolecular interactions. The chapter ends by setting the stage for the present investigations. The chapter two of the Thesis saddled with the task of describing the methodology employed in this Thesis begins by setting the stage on the importance of computational chemistry in interstellar chemistry. It discusses the Gaussian 09 suite of programs and the various theoretical methods used in all the quantum chemical calculations reported in this Thesis. The chapter ends with a brief summary on the homebuilt Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer used for the preliminary studies on Isoprene...Argon weakly bound complex reported in the appendix. After the introductory chapters, chapter three begins with what is unarguably one of the most important classes of interstellar molecular species - 'interstellar isomers'. In this chapter, the Energy, Stability and Abundance (ESA) relationship existing among interstellar molecular species has been firmly established using accurate thermochemical parameters obtained with the composite models and reported observational data. From the relationship, “Interstellar abundances of related species are directly proportional to their stabilities in the absence of the effect of interstellar hydrogen bonding”. The immediate consequences of the relationship in addressing some of the questions in interstellar chemistry such as: Where are Cyclic Interstellar Molecules? What are the possible candidates for astronomical observation? Why are more Interstellar Cyanides than isocyanides? among others are briefly discussed. Following the ESA relationship, other studies addressing some of the whys and wherefores in interstellar chemistry are discussed in details. From ESA relationship, though there has not been any successful astronomical observation of any heterocycle, the ones so far searched remain the best candidates for astronomical observation in their respective isomeric groups. The observation of the first branched chain molecule in ISM is in agreement with the ESA relationship and the C5H9N isomers have been shown to contain potential branched chain interstellar molecules. That molecules with the C-C-O backbone have less potential of formation in ISM as compared to their counterparts with the C-O-C backbone has been demonstrated not to be true following the ESA relationship. A detailed investigation on the relationship between molecular partition function and astronomical detection of isomeric species (or related molecules) shows that there is no direct correlation between the two rather there is a direct link between the thermodynamic stability of the isomeric species (or related molecules) and their interstellar abundances which influences the astronomical observation of some isomers at the expense of others. Chapter four presents an interesting and a fascinating phenomenon among the interstellar molecular species as it discusses for the first time, the existence and effects of Interstellar Hydrogen Bonding. This interstellar hydrogen bonding is shown to be responsible for the deviations from thermodynamically controlled processes, delayed observation of the most stable isomers, unsuccessful observations of amino acids among other happenings in interstellar chemistry and related areas. On the prediction that ketenes are the right candidates for astronomical searches among their respective isomers, a ketenyl radical; HCCO has recently been detected in line with this prediction. The deviation from the rule that the ratio of an interstellar sulphur molecule to its oxygen analogue is close to the cosmic S/O ratio is well accounted for on the basis of hydrogen bonding on the surface of the dust grains. Detecting weakly bound complexes in ISM has not been a major interest in the field so far but the detectability of weakly bound complexes in ISM is very possible as discussed in this chapter. Following the conditions in which these complexes are observed in the terrestrial laboratory as compared to the ISM conditions; it suffices to say that weakly bound complexes are present and are detectable in ISM. They could even account for some of the 'U' lines. Chapter five of the Thesis discusses the Linear Interstellar Carbon Chains which are the dominant theme in interstellar chemistry accounting for over 20% of all the known interstellar and circumstellar molecular species. Accurate spectroscopic parameters within experimental accuracy of few kHz which are the indispensable tools for the astronomical observation of these molecular species; are obtained for over 200 different species from the various chains using an inexpensive combined experimental and theoretical approach. With the availability of the spectroscopic parameters; thermodynamics is utilized in accounting for the known systems and in examining the right candidates for astronomical searches. These molecular species are shown to also obey the ESA relationship observed for the isomeric species discussed in chapter three of this work. The effect of kinetics on the formation processes of these molecular species is well controlled by thermodynamics as discussed in this chapter. Finally, the application of these studies in reducing the 'U' lines and probing new molecular species has been briefly summarized. Chapter six discusses Interstellar Ions and Isotopologues which are two unique classes of interstellar molecular species. Different studies on interstellar ions and isotopologues are presented. From the studies on interstellar protonated species with over 100 molecular species; protonated species resulting from a high proton affinity prefers to remain protonated rather than transferring a proton and returning to its neutral form as compared to its analogue that gives rise to a lower proton affinity from the same neutral species. The studies on detectable interstellar anions account for the known interstellar anions and predict members of the C2nO-, C2nS-, C2n-1Si-, HC2nN-, CnP-, and C2n chains as outstanding candidates for astronomical observation including the higher members of the C2nH- and C2n-1N- groups whose lower members have been observed. From high level ab initio quantum chemical calculations; ZPE and Boltzmann factor have been used to explain the observed deuterium enhancement and the possibility of detecting more deuterated species in ISM. Though all the heterocycles that have so far been searched for in ISM have been shown to be the right candidates for astronomical observation as discussed in the ESA relationship, they have also been shown to be strongly bonded to the surface of the interstellar dust grains thereby reducing their abundances, thus, contributing to their unsuccessful detection except for furan which is less affected by hydrogen bonding. The D-analogues of the heterocycles are shown from the computed Boltzmann factor to be formed under the dense molecular cloud conditions where major deuterium fractionation dominates implying very high D/H ratio above the cosmic D/H ratio which suggests the detectability of these deuterated species. Chapter seven examines the isomerization of the most stable isomer (which is probably the most abundant) to the less stable isomer(s) as one of the plausible formation routes for interstellar molecular species. An extensive investigation on the isomerization enthalpies of 243 molecular species from 64 isomeric groups is reported. From the results, the high abundances of the most stable isomers coupled with the energy sources in interstellar medium drive the isomerization process even for relative enthalpy difference as high as 67.4 kcal/mol. Specifically, the cyanides and their corresponding isocyanides pairs appear to be effectively synthesized via this process. The following potential interstellar molecules; CNC, NCCP, c-C5H, methylene ketene, methyl Ketene, CH3SCH3, C5O, 1,1-ethanediol, propanoic acid, propan-2-ol and propanol are identified and discussed. In all the isomeric groups, isomerization appears to be an effective route for the formation of the less stable isomers (which are probably less abundant) from the most stable ones. Chapter eight summarizes the conclusions drawn from the different studies presented in this Thesis and also highlights some of the future directions of these studies. The first appendix presents the preliminary study on Isoprene...Ar weakly bound complex while the second appendix contains a study on interstellar C3S describing the importance of accurate dipole moment in calculating interstellar abundances of molecular species and in astrophysical and astronomical models.

Initiated with the purpose of assigning the Fraunhofer lines in the solar spectrum to atomic transitions in the 18th century, the collaboration between spectroscopists and astrophysicists has remained fruitful, successful and ever fascinating. This collaboration has resulted in the unique detection of over 200 different molecular species in the interstellar medium (ISM). These interstellar molecular species play significant roles in diverse fields such as atmospheric chemistry, astrochemistry, prebiotic chemistry, astrophysics, astronomy, astrobiology, etc, and in our understanding of the solar system ''the world around us''. This Thesis work focuses on understanding of the different aspects of the chemistry of the various classes of these molecular species. Chapter one starts with an historical perspective of what is now regarded as Molecular Astrophysics or Astrochemistry and discusses the interstellar medium and its properties; interstellar molecular species and their importance; molecular spectroscopy as an indispensible tool in interstellar chemistry and the different formation routes of these molecular species. It also discusses hydrogen bonding which is one of the most important of all the intermolecular interactions. The chapter ends by setting the stage for the present investigations. The chapter two of the Thesis saddled with the task of describing the methodology employed in this Thesis begins by setting the stage on the importance of computational chemistry in interstellar chemistry. It discusses the Gaussian 09 suite of programs and the various theoretical methods used in all the quantum chemical calculations reported in this Thesis. The chapter ends with a brief summary on the homebuilt Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer used for the preliminary studies on Isoprene...Argon weakly bound complex reported in the appendix. After the introductory chapters, chapter three begins with what is unarguably one of the most important classes of interstellar molecular species - 'interstellar isomers'. In this chapter, the Energy, Stability and Abundance (ESA) relationship existing among interstellar molecular species has been firmly established using accurate thermochemical parameters obtained with the composite models and reported observational data. From the relationship, “Interstellar abundances of related species are directly proportional to their stabilities in the absence of the effect of interstellar hydrogen bonding”. The immediate consequences of the relationship in addressing some of the questions in interstellar chemistry such as: Where are Cyclic Interstellar Molecules? What are the possible candidates for astronomical observation? Why are more Interstellar Cyanides than isocyanides? among others are briefly discussed. Following the ESA relationship, other studies addressing some of the whys and wherefores in interstellar chemistry are discussed in details. From ESA relationship, though there has not been any successful astronomical observation of any heterocycle, the ones so far searched remain the best candidates for astronomical observation in their respective isomeric groups. The observation of the first branched chain molecule in ISM is in agreement with the ESA relationship and the C5H9N isomers have been shown to contain potential branched chain interstellar molecules. That molecules with the C-C-O backbone have less potential of formation in ISM as compared to their counterparts with the C-O-C backbone has been demonstrated not to be true following the ESA relationship. A detailed investigation on the relationship between molecular partition function and astronomical detection of isomeric species (or related molecules) shows that there is no direct correlation between the two rather there is a direct link between the thermodynamic stability of the isomeric species (or related molecules) and their interstellar abundances which influences the astronomical observation of some isomers at the expense of others. Chapter four presents an interesting and a fascinating phenomenon among the interstellar molecular species as it discusses for the first time, the existence and effects of Interstellar Hydrogen Bonding. This interstellar hydrogen bonding is shown to be responsible for the deviations from thermodynamically controlled processes, delayed observation of the most stable isomers, unsuccessful observations of amino acids among other happenings in interstellar chemistry and related areas. On the prediction that ketenes are the right candidates for astronomical searches among their respective isomers, a ketenyl radical; HCCO has recently been detected in line with this prediction. The deviation from the rule that the ratio of an interstellar sulphur molecule to its oxygen analogue is close to the cosmic S/O ratio is well accounted for on the basis of hydrogen bonding on the surface of the dust grains. Detecting weakly bound complexes in ISM has not been a major interest in the field so far but the detectability of weakly bound complexes in ISM is very possible as discussed in this chapter. Following the conditions in which these complexes are observed in the terrestrial laboratory as compared to the ISM conditions; it suffices to say that weakly bound complexes are present and are detectable in ISM. They could even account for some of the 'U' lines. Chapter five of the Thesis discusses the Linear Interstellar Carbon Chains which are the dominant theme in interstellar chemistry accounting for over 20% of all the known interstellar and circumstellar molecular species. Accurate spectroscopic parameters within experimental accuracy of few kHz which are the indispensable tools for the astronomical observation of these molecular species; are obtained for over 200 different species from the various chains using an inexpensive combined experimental and theoretical approach. With the availability of the spectroscopic parameters; thermodynamics is utilized in accounting for the known systems and in examining the right candidates for astronomical searches. These molecular species are shown to also obey the ESA relationship observed for the isomeric species discussed in chapter three of this work. The effect of kinetics on the formation processes of these molecular species is well controlled by thermodynamics as discussed in this chapter. Finally, the application of these studies in reducing the 'U' lines and probing new molecular species has been briefly summarized. Chapter six discusses Interstellar Ions and Isotopologues which are two unique classes of interstellar molecular species. Different studies on interstellar ions and isotopologues are presented. From the studies on interstellar protonated species with over 100 molecular species; protonated species resulting from a high proton affinity prefers to remain protonated rather than transferring a proton and returning to its neutral form as compared to its analogue that gives rise to a lower proton affinity from the same neutral species. The studies on detectable interstellar anions account for the known interstellar anions and predict members of the C2nO-, C2nS-, C2n-1Si-, HC2nN-, CnP-, and C2n chains as outstanding candidates for astronomical observation including the higher members of the C2nH- and C2n-1N- groups whose lower members have been observed. From high level ab initio quantum chemical calculations; ZPE and Boltzmann factor have been used to explain the observed deuterium enhancement and the possibility of detecting more deuterated species in ISM. Though all the heterocycles that have so far been searched for in ISM have been shown to be the right candidates for astronomical observation as discussed in the ESA relationship, they have also been shown to be strongly bonded to the surface of the interstellar dust grains thereby reducing their abundances, thus, contributing to their unsuccessful detection except for furan which is less affected by hydrogen bonding. The D-analogues of the heterocycles are shown from the computed Boltzmann factor to be formed under the dense molecular cloud conditions where major deuterium fractionation dominates implying very high D/H ratio above the cosmic D/H ratio which suggests the detectability of these deuterated species. Chapter seven examines the isomerization of the most stable isomer (which is probably the most abundant) to the less stable isomer(s) as one of the plausible formation routes for interstellar molecular species. An extensive investigation on the isomerization enthalpies of 243 molecular species from 64 isomeric groups is reported. From the results, the high abundances of the most stable isomers coupled with the energy sources in interstellar medium drive the isomerization process even for relative enthalpy difference as high as 67.4 kcal/mol. Specifically, the cyanides and their corresponding isocyanides pairs appear to be effectively synthesized via this process. The following potential interstellar molecules; CNC, NCCP, c-C5H, methylene ketene, methyl Ketene, CH3SCH3, C5O, 1,1-ethanediol, propanoic acid, propan-2-ol and propanol are identified and discussed. In all the isomeric groups, isomerization appears to be an effective route for the formation of the less stable isomers (which are probably less abundant) from the most stable ones. Chapter eight summarizes the conclusions drawn from the different studies presented in this Thesis and also highlights some of the future directions of these studies. The first appendix presents the preliminary study on Isoprene...Ar weakly bound complex while the second appendix contains a study on interstellar C3S describing the importance of accurate dipole moment in calculating interstellar abundances of molecular species and in astrophysical and astronomical models.