Littérature scientifique sur le sujet « Spectroscopic Study - Weakly Bound Molecules/Complexes »

In the present work, complexes of DNA with nano-clay montmorillonite (Mt) were investigated by means of atomic force microscopy (AFM) under various conditions. In contrast to the integral methods of analysis of the sorption of DNA on clay, AFM allowed us to study this process at the molecular level in detail. DNA molecules in the deionized water were shown to form a 2D fiber network weakly bound to both Mt and mica. The binding sites are mostly along Mt edges. The addition of Mg2+ cations led to the separation of DNA fibers into separate molecules, which bound mainly to the edge joints of the Mt particles according to our reactivity estimations. After the incubation of DNA with Mg2+, the DNA fibers were capable of wrapping around the Mt particles and were weakly bound to the Mt edge surfaces. The reversible sorption of nucleic acids onto the Mt surface allows it to be used for both RNA and DNA isolation for further reverse transcription and polymerase chain reaction (PCR). Our results show that the strongest binding sites for DNA are the edge joints of Mt particles.

A vibronic level study of the spectroscopy and photophysics of the C6H6–CHCl3 complex has been carried out using a combination of laser-induced fluorescence and resonant two-photon ionization (R2PI). In C6H6-CHCl3, the S1–S0 origin remains forbidden while the 1610 transition is weakly induced. Neither 610 nor 1610 are split by the presence of the CHCl3 molecule. On this basis, a C3vstructure is deduced for the complex, placing CHCl3 on the six-fold axis of benzene. The large blue-shift of the complex’s absorption relative to benzene (+178 cm–1) and the efficient fragmentation of the complex following one-color R2PI reflect a hydrogen-bonded orientation for CHCl3 relative to benzene’ π cloud. Dispersed fluorescence scans place a firm upper bound on the ground state binding energy of the complex of 2,024 cm–1. Both the 61and 61 11 levels do not dissociate on the time-scale of the S1 fluorescence and show evidence of extensive state mixing with van der Waals’ levels primarily built on the 00 level of benzene. The C6H6–(CHCl3)2 cluster shows extensive intermolecular structure beginning at +84 cm–1, a strong origin transition, and splitting of 61. A structure which places both CHCl3 molecules on the same side of the benzene ring is suggested on this basis. The vibronic level scheme used to deduce the structure of C6H6–CHCl3 is tested against previous data on other C6H6–X complexes. The scheme is found to be capable, in favorable cases, of deducing the structures of C6H6–X complexes based purely on vibronic level data. Finally, the results on C6H6–CHCl3 are compared with those on C6H6–HCl and C6H6-H2O to evaluate the characteristics of the n hydrogen bond.

Abstract Syntheses and room-temperature single crystal X-ray structure determinations are recorded for an array of complexes formed between copper(I) perchlorate and benzonitrile of CuClO4 : PhCN (1:n) stoichiometry. Copper(I) perchlorate crystallized from neat benzonitrile solution yields a 1:5 CuClO4 : PhCN adduct, shown by the X-ray study to be of the form [Cu(NCPh)4](ClO4). PhCN, and, on recrystallization from dichloromethane, the 1:4 adduct, shown to be [Cu(NCPh)4](ClO4), the copper(I) atom in both the n = 4,5 adducts being in a quasi-tetrahedral four-coordinate environment, < Cu−N > 1.99 Å . Heating of either of the above materials under vacuum to 70 - 80◦ or 85 - 90 ◦C (Care!) yields 1:3 and 1:2 adducts respectively which may be crystallized from dichloromethane. The 1:3 adduct is shown to be of the form [(PhCN)3Cu(OClO3)], the CuN3 array quasi-trigonal planar (Σ N-Cu-N 358.0 ◦; Cu-N 1.906(4)-1.958(4), <> 1.93 Å ), with a long unidentate perchlorate oxygen approach (Cu. . .O 2.404(4) Å). The 1:2 adduct comprises a pair of quasi-linear [(PhCN)Cu(NCPh)] moieties (Cu-N 1.884(6), 1.866(5) Å ; N-Cu-N 158.6(3)◦] linked about an inversion centre by a pair of oxygen atoms from centrosymmetrically related perchlorate groups, so that a weakly bound fourmembered Cu(μ-O)2Cu central ring is obtained (Cu. . .O 2.445(4), 2.502(6) Å ). The structural data provide a basis for a comprehensive vibrational spectroscopic study across the whole array. These spectra show features that can be attributed to the structural changes that are observed with the change in the number of benzonitrile molecules in the compounds. The vibrational spectra of the acetonitrile complex [Cu(NCMe)4](ClO4) have also been recorded and used to assist in the assignment of the spectra of the various stoichiometries of the benzonitrile compounds.

AbstractIn this work we present the results of high level ab initio calculations on weakly bound complexes of aluminium trichloride and hydrogen halides, HX, halogens, X2 and diatomic interhalogens, XY (where X, Y = F, Cl, Br). Based upon these calculations we have predicted that all structures in the staggered conformation (except for Cl3AlFH and Cl3AlClH) are stable minima while those in the eclipsed configurations are transition state structures. In the XH complexes the strength of interaction with the Cl3Al group is FH &gt; ClH &gt; BrH. In the case of X2 species it is Br2 &gt; F2 &gt; Cl2, and finally in the XY (YX) group it is: FBr &gt; ClBr &gt; FCl &gt; BrCl &gt; BrF &gt; ClF.

AbstractThe electronic and geometric structure, stability and molecular properties of the cationic van-der-Waals complex Ar2H+ in its ground electronic state are studied by means of two ab-initio quantum-chemical approaches: conventional configuration interaction (multi-reference and coupled-cluster methods) and a diatomics-in-molecules model with ab-initio input data. To ensure consistency between the two approaches, one and the same one-electron atomic basis set (aug-cc-pVTZ by Dunning) is employed in both. The topography of the ground-state potential-energy surface is examined with respect to the nature of the binding and the stability of structures corresponding to stationary points. In accordance with most earlier theoretical work, there are two local minima at linear arrangements: a strongly bound centro-symmetric moiety, (Ar–H–Ar)+, and a weakly bound van-der-Waals complex, Ar···ArH+. These are separated by a low barrier. Only the centro-symmetric molecule is significantly stable (De = 0.68eV) against fragmentation into Ar + ArH+ and should have structural and dynamical relevance. A fairly simple diatomics-in-molecules model taking into account only the few lowest electronic fragment states yields a qualitatively correct description of the ground state but shows quantitative deviations from the more accurate configuration-interaction data in detail. Nevertheless, it should provide a good starting point for the treatment of larger complexes ArnH+ with n > 2.

Multidimensional potential energy surfaces for heavy noble gas–propylene oxide systems are obtained by applying the phenomenological method successfully used to describe homologous systems involving He and Ne atoms. Such potential energy surfaces, where the interaction exclusively arises from the anisotropic van der Waals interaction components, are given in an analytical form. Therefore, they can be easily used as force fields to carry out molecular simulations to evaluate spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide (a prototype chiral species) with a noble gas atom (a prototype isotropic partner) by two-body collisions under a variety of conditions. Several potential energy minima are identified on the surfaces, which are confirmed and characterized by high level ab initio calculations. The next step to further generalize this methodology is its extension to systems involving propylene oxide-diatomic molecules (as H2, O2 and N2), as well as to propylene oxide dimers.

In this study, the interaction of native and transglutaminase (Tgase) cross-linked β-lactoglobulin (β-LG) with caffeic acid (CA) was examined, aiming to obtain functional composites. Knowledge on the binding affinity and interaction mechanism was provided by performing fluorescence spectroscopy measurements, after heating the native and cross-linked protein at temperatures ranging from 25 to 95 °C. Regardless of the protein aggregation state, a static quenching mechanism of intrinsic fluorescence of β-LG by CA was established. The decrease of the Stern–Volmer constants with the temperature increase indicating the facile dissociation of the weakly bound complexes. The thermodynamic analysis suggested the existence of multiple contact types, such as Van der Waals’ force and hydrogen bonds, between β-LG and CA. Further molecular docking tests indicated the existence of various CA binding sites on the β-LG surface heat-treated at different temperatures. Anyway, regardless of the simulated temperature, the CA-β-LG assemblies appeared to be unstable. Compared to native protein, the CA-β-LG and CA-β-LGTgase complexes (ratio 1:1) exhibited significantly higher antioxidant activity and inhibitory effects on α-glucosidase, α-amylase, and pancreatic lipase, enzymes associated with metabolic syndrome. These findings might help the knowledge-based development of novel food ingredients with valuable biological properties.

The purpose of this study was to increase the dissolution of glycyrrhetinic acid (GA) by preparing ternary solid dispersion (TSD) systems containing alkalizers, and to explore the modulating mechanism of alkalizers in solid dispersion systems. GA TSDs were prepared by hot melt extrusion (HME) with Kollidon® VA64 as the carrier and L-arginine/meglumine as the alkalizers. The in vitro release of the TSD was investigated with a dissolution test, and the dissociation constant (pKa) was used to describe the ionization degree of the drug in different pH buffers. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), Fourier Transform Infrared Spectroscopy (FTIR), Raman spectra, X-ray photoelectron spectroscopy (XPS), and a molecular model were used for solid-state characterizations and to study the dissolution mechanism of the TSDs. It was evident that the dissolution of GA significantly increased as a result of the TSD compared to the pure drug and binary solid dispersion. SEM, DSC, and XPRD data showed that GA transformed into an amorphous form in TSD. As illustrated by FTIR, Raman, XPS, and molecular docking, high binding energy ion-pair complexes formed between GA and the alkalizers during the process of HME. These can destroy the H-bond between GA molecules. Further, intermolecular H-bonds formed between the alkalizers and Kollidon® VA64, which can increase the wettability of the drug. Our results will significantly improve the solubility and dissolution of GA. In addition, the lower pKa value of TSD indicates that higher ionization is beneficial to the dissolution of the drug. This study should facilitate further developments of TSDs containing alkalizers to improve the dissolution of weakly acidic drugs and gain a richer understanding of the mechanism of dissolution.

This work provides new insight into assembling of phenol in various solvents and competition between different kinds of interactions. To examine both weak and strong interactions, we selected a series of non-aromatic and aromatic solvents. Infrared spectra were measured at low (0.05 M) and high (2 M) phenol content. In addition, we performed density functional theory calculations of the structures and harmonic vibrational spectra of 1:1 complexes of phenol with the solvents and the associates of phenol from dimer to tetramer. Based on these results, we divided the solvents into three groups. The first group consists of non-aromatic solvents weakly interacting with phenol. Depending on the concentration, molecules of phenol in these solvents remain non-bonded or self-associated. In diluted solutions of phenol in chlorinated non-aromatic solvents do not appear free OH groups, since they are involved in a weak OH···Cl interaction. It is of note that in diluted solutions of phenol in tetramethyl ethylene both the non-bonded and bonded OH coexists due to solvent–solvent interactions. The second group consists of aromatic solvents with methyl or chlorine substituents. At low concentration, the molecules of phenol are involved in the phenol–solvent OH···π interaction and the strength of these interactions depends on the solvent properties. At a higher phenol content an equilibrium exists between phenol–solvent OH···π and phenol–phenol OH···OH interactions. Finally, the third group includes the aromatic and non-aromatic solvents with highly polar group (C≡N). In these solvents, regardless of the concentration all molecules of phenol are involved in the solute–solvent OH···NC interaction. Comparison of the experimental and theoretical band parameters reveals that molecules of phenol in non-aromatic solvents prefer the cyclic associates, while in the aromatic solvents they tend to form the linear associates.

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.

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.

During the past decade, the study of photoinitiated reactive and inelastic processes within weakly bound gaseous complexes has evolved into an active area of research in the field of chemical physics. Such specialized microscopic environments offer a number of unique opportunities which enable scientists to examine regiospecific interactions at a level of detail and precision that invites rigorous comparisons between experiment and theory. Specifically, many issues that lie at the heart of physical chemistry, such as reaction probabilities, chemical branching ratios, rates and dynamics of elementary chemical processes, curve crossings, caging, recombination, vibrational redistribution and predissociation, etc., can be studied at the state-to-state level and in real time. Inevitably, understanding the photophysics and photochemistry of weakly bound complexes lends insight into corresponding processes in less rarefied surroundings, for example, molecules physisorbed on crystalline insulator and metal surfaces, molecules residing on the surfaces of various ices, and molecules weakly solvated in liquids. However, such ties to the real world are not the main driving force behind studies of photoinitiated reactions in complexed gaseous media. Rather, it is the lure of going a step beyond the more common molecular environments. Theoretical modeling, which in many areas purports to challenge experiment, must rise to the occasion here if it is to offer predictive capability for even the simplest of such microcosms. Subtleties abound. Roughly speaking, two disparate regimes can be identified which are accessible experimentally and which correspond to qualitatively different kinds of chemical transformations. These are distinguished by their reactants: electronically excited versus ground state. For example, it is possible to study the chemical selectivity that derives from the alignment and orientation of excited electronic orbitals, albeit at restricted sets of nuclear coordinates. This is achieved by electronically exciting a complexed moiety, such as a metal atom, which then undergoes chemical transformations that depend on the geometric properties of the electronic orbitals such as their alignments and orientations relative to the other moiety (or moieties) in the complex.

Thermodynamic studies provide information that is necessary in order to understand the forces that drive the formation of ligand-macromolecule complexes. Knowledge of the energetics of these interactions is also indispensable for characterization of functionally important structural changes that occur within the studied complexes. Quantitative examination of the equilibrium interactions are designed to provide the answers to the questions: What is the stoichiometry of the formed complexes? How strong or how specific are the interactions? Are there any cooperative interactions among the binding sites and/or the bound ligand molecules? Are the binding sites intrinsically heterogeneous? What are the molecular forces involved in the formation of the studied complexes, or, in other words, how do the equilibrium binding and kinetic parameters depend on solution variables (temperature, pressure, pH, salt concentration, etc.)? Equilibrium isotherms for the binding of a ligand to a macromolecule represent the relationship between the degree of ligand binding (moles of ligands bound per mole of a macromolecule) and the free ligand concentration. A true thermodynamic binding isotherm is model-independent and reflects only this relationship. Only then, when such an isotherm is obtained, can one proceed to extract physically meaningful interaction parameters that characterize the free energies of interaction. This is accomplished by comparing the experimental isotherms to theoretical predictions based on specific binding models that incorporate known molecular aspects, such as intrinsic binding constants, cooperativity parameters, allosteric equilibrium constants, discrete character of the binding sites or overlap of potential binding sites, etc. (see below). Any method used to quantitatively study ligand binding to a macromolecule must relate the extent of the complex formation to the free ligand concentration in solution. Numerous techniques have been developed to study equilibrium properties of specific and non-specific ligand-macromolecule interactions in which binding is directly monitored, including equilibrium dialysis, ultrafiltration, column chromatography, filter binding assay and gel electrophoresis (1-6). These direct methods are very straightforward; however, they are usually time consuming and some, like filter binding or gel shift assays, are non-equilibrium techniques which require many controls before the reliable equilibrium binding data can be obtained.

Infrared laser spectroscopy has become a powerful tool in the study of weakly bound molecular complexes. The molecular constants obtained from these spectra can be used to determine the "structure" of the complex, for systems where this is a meaningful concept, while, in complexes which undergo wide amplitude excursions from their equilibrium geometries, the spectroscopy is often sensitive to the details of the intermolecular potential energy surface. In many cases, these spectra are sensitive to both the internal dynamics of the complex and the vibrational predissociation dynamics that result from the excitation process.

In condensed media, chemical reactions can be initiated with a great deal of geometric specificity, since the forces holding the molecules in place ensure that the reactants are aligned and oriented relative to one another. Unfortunately, the surrounding medium is in constant interaction with the reactive site and no signature characteristic of the eigenstates of isolated product species can be obtained. On the other hand, binary encounters in the gas phase are especially well suited for detecting nascent excitations. However, with isotropic samples the initial conditions are unbiased so that all angles and impact parameters are present. To exploit the virtues of each of these environments, we use weakly bound van der Waals-type complexes as precursors for studying elementary processes. A prototypical example is CO2 HBr, where the potential is minimum with the nuclei along a straight line. These complexes are prepared at 2K by supersonic expansion, and photodissociation of the HBr constituent propels the H-atom toward the CO2 with initial alignment, etc., determined mainly by zero-point fluctuations of the complex. Nascent products (e.g., OH, CO) can be detected by standard spectroscopic methods before collisions become troublesome. The technique can be used to peruse the system’s ability to avoid low energy channels (e.g., with an SCOHX precursor, can OH + CS be favored over SH + CO?), as well as provide stringent tests for different kinds of calculation.