Vibrational predissociation in the HCl dimer

We present results of a combined theoretical and experimental study on the vibrational predissociation of the HCl dimer. On the theoretical side, photodissociation linewidths and product-state distributions for monomer stretch excited states with total angular momentum J=0 were computed, using the Fermi golden rule approximation. The resonances investigated include excitation of the hydrogen bond donor and acceptor stretches, as well as combinations of one of these modes with the intermolecular stretch and geared bend modes, for both even and odd permutation symmetry. Line strengths for the transitions from the J=1, K=0 ground state to excited states with J=0 were computed using quasibound states. On the experimental side, the photofragment angular distribution method was employed to obtain complete final-state distributions for the monomer stretch excited states. Three different transitions were probed, all starting from the lower tunneling component of the ground state: the (R)Q(0)(1) transition for excitation of the acceptor stretch and the (Q)R(0)(0) transition and unresolved (R)Q(0) branch for the donor stretch excitation. We find that, in contrast to the HF dimer, the excited-state alignment of the HCl dimer, resulting from excitation using a polarized laser beam, is completely lost on the time scale of the dissociation. The agreement between theory and experiment for the product-state distributions and line strengths is reasonable. The computed lifetimes are 1-2 orders of magnitude too small, which is attributed to a deficiency in the potential energy surface.     

Infrared Spectroscopy of Neutral and Cationic Pyrrolidine Monomer in Supersonic Jet

Pyrrolidine, a five membered heterocyclic molecule, is widely existing in organism. Herein, infrared spectra of pyrrolidine monomer in neutral and cationic states were obtained by vacuum ultraviolet ionization, infrared photodissociation and time of flight mass spectrometry. Both in neutral and cationic states, it is found that their CH stretching vibration bands are red shifted. In the IR spectrum of neutral pyrrolidine, because the electric dipole moment of NH is small, we have not observed the NH stretching vibration bands. However, the NH stretching vibration band of pyrrolidine is greatly enhanced after ionization, and this band red-shifts compared with the previous experiment. The red shifts of CH stretching vibrations in neutral and cationic states are caused by the negative and positive hyperconjugation, respectively. The enhancement and red shift of the NH stretching band are owing to the ejection of the electrons on the N atom after ionization. Through the calculations, it is found that the acidity of the CH bond is a little stronger than that of NH bond. These kinds of studies would be helpful to understand the intrinsic properties of biomolecules in neutral and cationic states, and to provide reference for the further study of living organic macromolecules.     

Structure of 7-azaindole···2-fluoropyridine dimer in a supersonic jet: competition between N-H···N and N-H···F interactions

In the present work, we have investigated the structure of 7-azaindole···2-fluoropyridine dimer in a supersonic jet by employing resonant two photon ionization (R2PI), IR-UV, and UV-UV double resonance spectroscopic techniques combined with quantum chemistry calculations. The R2PI spectrum of the dimer is recorded by electronic excitation of the 7-azaindole moiety, and a few low frequency intermolecular vibrations of the dimer are clearly observed in the spectrum. The electronic origin band of the dimer is red-shifted by 1278 cm(-1) from the S(1) ← S(0) origin band of 7-azaindole monomer. The presence of a single conformer of the dimer is confirmed by IR-UV and UV-UV hole-burning spectroscopic techniques. RIDIR (Resonant ion dip infrared) spectrum of the dimer shows a red-shift of 265 cm(-1) in the N-H stretching frequency with respect to that of the 7-azaindole monomer. Two planar double hydrogen bonded cyclic structures of the dimer have been predicted from DFT calculations. Comparison of experimental and theoretical N-H stretching frequencies confirms that the observed dimer is stabilized by N-H···N and C-H···N hydrogen bonding interactions. The less stable conformer with N-H···F and C-H···N interactions are not observed in the experiment. The competition between N-H···N and N-H···F interactions in the two dimeric structures are discussed from natural bond orbital (NBO) analysis. The current results demonstrate that fluorine makes a hydrogen bond of intermediate strength through cooperative interaction of another hydrogen bond (C-H···N) present in the dimer, although fluorine is believed to be very weak hydrogen bond acceptor.     

Ab initio theoretical calculations of the electronic excitation energies of small water clusters

A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.     

A Theoretical Study on Hydrogen‐Bonded Complex of Proflavine Cation and Water: The Site‐dependent Feature of Hydrogen Bond Strengthening and Weakening

The intermolecular hydrogen‐bonds between proflavine cation (PC) and water molecules are investigated by density functional theory (DFT) and time‐dependent density functional theory (TDDFT) methods. The ground‐state geometry optimizations, electronic excitation energies and corresponding oscillation strengths of the low‐lying electronically excited states for the isolated proflavine cation, the hydrogen‐bonded PC–H2O dimer and PC–(H2O)2 trimer are calculated. Intermolecular hydrogen bonds at the central site of proflavine molecule are found to be stronger than the peripheral site. The hydrogen bond N–H???O for the hydrogen‐bonded dimer are indicated to be weakened in the excited states, since the excitation energy is increased slightly comparing to the monomer. Hydrogen bonds of PC–(H2O)2 trimer with the same type as the dimer are strengthened in the excited state, which is demonstrated by the decrease of the excited energies. Thus, hydrogen bond strengthening and weakening are observed to reveal site dependent feature in proflavine molecule. Furthermore, the hydrogen bond at central site induces the blue‐shift of the absorption spectrum, while the ones at peripheral site induce red‐shift. Hydrogen bonds with the same type at peripheral and central sites of proflavine molecule provide different effects on the photochemical and photophysical properties of proflavine.     

Theory of the photodissociation of ozone in the Hartley continuum; effect of vibrational excitation and O(1D) atom velocity distribution

The effect of vibrational excitation on the photodissociation cross section of ozone in the Hartley continuum is examined. The calculations make use of newly computed potential energy and transition dipole moment surfaces. The initial vibrational states of the ozone are computed using grid based techniques and the first few ab initio computed vibrational energy level spacings agree to within 10 cm(-1) with experimental values. The computed total absorption cross sections arising from different initial vibrational states of ozone are discussed in the light of the nature of the transition dipole moment surface. The computed cross section for excitation from the ground vibrational-rotational state is in good agreement with the experimentally measured cross section. Excitation of the asymmetric stretching vibration of ozone has a marked effect on both the form and magnitude of the photodissociation cross section. The velocity distributions of highly reactive O(1D) atoms arising from the photodissociation process in different wavelength ranges is also presented. The results show that the O(1D) atoms travel with a most probable translational velocity of 2.030 km s(-1) corresponding to a translational energy of 0.342 eV or 33.0 kJ mol(-1).     

Infrared matrix isolation and quantum chemical studies of the nitrous acid complexes with water

The 1:1 and 2:1 complexes between water and trans- and cis-isomers of nitrous acid have been isolated in argon matrices and studied using FTIR spectroscopy and DFT(B3LYP) calculations with a 6-311++G(2d,2p) basis set. The analysis of the experimental spectra indicate that 1:1 complexes trapped in solid argon involve very strong hydrogen bond in which acid acts as the proton donor and water as the proton acceptor. The perturbed OH stretches are −248, −228 cm⁻¹ red shifted from their free-molecules values in complexes formed by trans- and cis-HONO isomers, respectively. The calculated spectral parameters for the two complexes are in good agreement with experimental data. The calculations also predict stability of two more 1:1 weakly bound complexes formed by each isomer. In these the water acts as the proton donor and one of the two oxygen atoms of the acid as the acceptor. The experimental spectra demonstrate also formation of 2:1 complex between water and trans-HONO isomer in an argon matrix. The performed calculations indicate that the complex involves a seven-membered ring in which OH group of HONO forms very strong hydrogen bond with the oxygen atom of one water molecule and nitrogen atom acts as a weak proton acceptor for the hydrogen atom of the second water molecule of the water dimer. The observed perturbations of the OH stretch of trans-HONO (750 cm⁻¹ red shift) is much larger than that predicted by calculations (556 cm⁻¹ red shift); this difference is attributed to strong solvation effect of argon matrix on very strong hydrogen bond.     

Photophysical Property of Photoactive Molecules with Multibranched Push-Pull Structures

The structure-property characteristics of a series of newly synthesized intramolecular charge-transfer (ICT) compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as acceptor, the corresponding two-branch dimer and three-branch trimer, have been investigated by means of steady-state and femtosecond time-resolved stimulated emission fluorescence depletion (FS TR-SEP FD) techniques in different polar solvents. The TD-DFT calculations are further performed to explain the observed ICT properties. The interpretation of the experimental results is based on the comparative stud-ies of the series of compounds which have increased amount of identical branch moiety. The similarity of the absorption and fluorescence spectra as well as strong solvent-dependence of the spectral properties for the three compounds reveal that the excited state of the dimer and trimer are nearly the same with that of the monomer, which may localize on one branch. It is found that polar excited state emerged through multidimensional intramolecular charge transfer from the donating moiety to the acceptor upon excitation, and quickly relaxed to one branch before emission. Even so, the red-shift in the absorption and emission spectra and decreased fluorescence radiative lifetime with respect to their monomer counterpart still suggest some extent delocalization of excited state in the dimer and trimer upon excitation. The similar behavior of their excited ICT state is demonstrated by FS TR-SEP FD mea-surements, and shows that the trimer has the largest charge-separate extent in all studied three samples. Finally, steady-state excitation anisotropy measurements has further been carried out to estimate the nature of the optical excitation and the mechanism of energy redistribution among the branches, where no plateau through the ICT band suggests the intramolecular excitation transfer process between the branches in dimer and trimer.     

N-H···π hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ～6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.     

Determination of the geometry change of the phenol dimer upon electronic excitation.

The change of the phenol dimer (PH2) structure upon electronic excitation is determined by a Franck-Condon analysis of the intensities in the fluorescence emission spectra obtained via excitation of seven different vibronic bands. A total of 547 emission band intensities are fitted, together with the changes of rotational constants upon electronic excitation of fi ve isotopomers. These rotational constants are taken from previously published [Schmitt et al. ChemPhysChem 2006, 7, 1241-1249] high-resolution LIF measurements. The geometry change upon electronic excitation of the pipi* state of the donor moiety can be described by a strong shortening of the hydrogen bond, a shortening of the CO bond in the donor moiety, an overall symmetric expansion of the donor phenol ring, and a nearly unchanged acceptor moiety. The resulting geometry changes are interpreted on the basis of ab initio calculations.     

Hydrated alizarin complexes: hydrogen bonding and proton transfer

We investigated the hydrogen bonding structures and proton transfer for the hydration complexes of alizarin (Az) produced in a supersonic jet using fluorescence excitation (FE), dispersed laser induced fluorescence (LIF), visible-visible hole burning (HB), and fluorescence detected infrared (FDIR) spectroscopy. The FDIR spectrum of bare Az with two O-H groups exhibits two vibrational bands at 3092 and 3579 cm(-1), which, respectively, correspond to the stretching vibration of O1-H1 that forms a strong intramolecular hydrogen bond with the C9=O9 carbonyl group and the stretching vibration of O2-H2 that is weakly hydrogen-bonded to O1-H1. For the 1:1 hydration complex Az(H(2)O)(1), we identified three conformers. In the most stable conformer, the water molecule forms hydrogen bonds with the O1-H1 and O2-H2 groups of Az as a proton donor and proton acceptor, respectively. In the other conformers, the water binds to the C10=O10 group in two nearly isoenergetic configurations. In contrast to the sharp vibronic peaks in the FE spectra of Az and Az(H(2)O)(1), only broad, structureless absorption was observed for Az(H(2)O)(n) (n≥ 2), indicating a facile decay process, possibly due to proton transfer in the electronic excited state. The FDIR spectrum with the wavelength of the probe laser fixed at the broad band exhibited a broad vibrational band near the O2-H2 stretching vibration frequency of the most stable conformer of Az(H(2)O)(1). With the help of theoretical calculations, we suggest that the broad vibrational band may represent the occurrence of proton transfer by tunnelling in the electronic ground state of Az(H(2)O)(n) (n≥ 2) upon excitation of the O2-H2 vibration.     

On the Correlation between the Blue Shift of Hydrogen Bonding and the Proton Donor-Proton Acceptor Distance

It is demonstrated that in all types of hydrogen bonds (X—H…Y) there is a balance between the long-range attractive orbital interactions and short-range Pauli/nucleus repulsions. When the proton acceptor approaches the proton donor from distance, the hydrogen bonding energy becomes more negative at relatively large distance, goes through a minimum, and then starts to become less negative when the short-range repulsive forces come into effect.Meanwhile, the X--H bond length increases at relatively large distances, goes through a maximum and starts to shorten when the short-range repulsive forces come into effect. Whether the hydrogen bond is red or blue shifted is dictated by the energy minimum position. If at the energy minimum position the X—H bond length is shorter than that for the free monomer, the hydrogen bond is blue shifted and vice versa. Further studies demonstrate that the recent report about the correlation of C—H bond lengths with proton donor-acceptor distance in F3C—H…OH2 and F3C—H…Cl^- is not fully correct because the authors conducted an inappropriate comparison. Furthermore, it is shown for the first time that the Pauli/nucleus repulsion theory is applicable to the blue-shifted hydrogen bonds in the X—H…π complexes and the blue-shifted lithium bonds in the X—Li…Y complexes.     

Frequency analysis of amide-linked rotaxane mimetics

A vibrational analysis of 2-fold hydrogen bonds between an isophthalic amide donor and different acceptors is presented. These systems can be considered as mimetics for the hydrogen-binding situation of numerous supramolecular compounds such as rotaxanes, catenanes, knotanes, and anion receptors. We calculated pronounced red-shifts up to 65 cm(-1) for the stretching modes of the acceptor carbonyl as well as for the donor NH2 groups, whereas we observe a blue shift for the NH2 bending modes and an additional weak hydrogen bond between the acceptor and the middle C-H group of the donor. The red and blue shifts observed for different modes in various complexes have been correlated with the binding energy of the complexes, independently. In comparison with comparable single hydrogen bonds, we find for the 2-fold hydrogen bonds smaller red shifts for the N-H stretch modes of the donor but larger red shifts for the C=O stretch mode of the acceptor. Furthermore, our results indicate that the pronounced blue shift of the C-H stretch mode is basically caused by the fact that the acceptor is fixed directly above this group due to the 2-fold hydrogen bond.     

Infrared spectroscopy of Cr+(H2O) and Cr2+(H2O): the role of charge in cation hydration

Singly and doubly charged chromium-water ion-molecule complexes are produced by laser vaporization in a pulsed-nozzle cluster source. These species are detected and mass-selected in a specially designed time-of-flight mass spectrometer. Vibrational spectroscopy is measured for these complexes in the O-H stretching region using infrared photodissociation spectroscopy and the method of rare gas atom predissociation. Infrared excitation is not able to break the ion-water bonds in these systems, but it leads to elimination of argon, providing an efficient mechanism for detecting the spectrum. The O-H stretches for both singly and doubly charged complexes are shifted to frequencies lower than those for the free water molecule, and the intensity of the symmetric stretch band is strongly enhanced relative to the asymmetric stretch. Partially resolved rotational structure for both complexes shows that the H-O-H bond angle is greater than it is in the free water molecule. These polarization-induced effects are enhanced in the doubly charged ion relative to its singly charged analog.     

Vibrational dynamics of the hydrogen bond in H(2)S-HF: Fourier-transform-infrared spectra and ab initio theory

The rotationally resolved infrared spectrum of the hydrogen bonded complex H(2)S-HF and of its isotopomer D(2)S-DF in the HF/DF stretching range have been observed in a supersonic jet Fourier-transform infrared (FTIR) experiment and indicate a predissociation lifetime of 130 ps for H(2)S-HF. Complementary spectra taken at a temperature of 190 K in a cell without resolved rotational structure indicate the presence of strong anharmonic couplings between low frequency intermolecular modes and the HF donor stretch mode previously observed in other complexes with heavier acceptor molecules without rotational fine structure. The anharmonic analysis of the hot band progressions and of the rotational data confirm the coupling mechanism. The coupling constants and the absolute frequency of the hydrogen bonded stretch mode are in excellent agreement with theoretical predictions based on adiabatic variational calculations on potential surfaces computed at MP2 and CCSD(T) level. Complementary calculations with a perturbational approach further confirm the coupling model.     

The structure of C2H4 clusters from theoretical interaction potentials and vibrational predissociation data

Optimized geometries and binding energies are calculated for ethene (ethylene) dimers, trimers, and tetramers based on a pairwise additive dimer potential. From these results intermolecular frequencies and relative abundancies (catchment areas) of the different isomers are obtained and compared with the results of accurate measurements of the photodissociation upon absorption of one photon of a CO₂ laser in the region of thev ₇ monomer absorption band at 949 cm^?1. The clusters are size selected in a scattering experiment and show for a cluster size fromn=2 ton=6 a frequency maximum shifted by 3 cm^?1 to the blue compared with the monomer. The result is explained by the predominance of chains and chain-like structures of the clusters in the photodissociation process. The chains consist of cross-like dimer sub-units.     

Structure and matrix isolation infrared spectrum of formyl fluoride dimer: blue-shift of the C-H stretching frequency

Infrared spectroscopy (IR) of formyl fluoride (HCOF) dimer is studied in low-temperature argon and krypton matrixes. New IR absorptions, ca. 17 cm(-1) blue shifted from the monomer C-H stretching fundamental, are assigned to the HCOF dimer. The MP2/6-311++G calculations were utilized to define structures and harmonic frequencies of various HCOF dimers. Among the four optimized structures, the dimer having two C-H...O hydrogen bonds possesses strongest intermolecular bonding. The calculated harmonic frequencies of this dimer structure are shifted from the monomer similarly as observed in the experiment. Thus, we suggest that the experimentally observed blue shifted C-H bands belong to the dimer with two C-H...O hydrogen bonds. This observation includes the HCOF dimer to the class of hydrogen bonded complexes showing blue shift in their vibrational energies.     

Measurement of the fourth O-H overtone absorption cross section in acetic acid using cavity ring-down spectroscopy

We report the absolute absorption cross sections of the fourth vibrational O-H (5ν(OH)) overtone in acetic acid using cavity ring-down spectroscopy. For compounds that undergo photodissociation via overtone excitation, such intensity information is required to calculate atmospheric photolysis rates. The fourth vibrational overtone of acetic acid is insufficiently energetic to effect dissociation, but measurement of its cross section provides a model for other overtone transitions that can affect atmospheric photochemistry. Though gas-phase acetic acid exists in equilibrium with its dimer, this work shows that only the monomeric species contributes to the acetic acid overtone spectrum. The absorption of acetic acid monomer peaks at ～615 nm and has a peak cross section of 1.84 × 10(-24) cm(2)·molecule(-1). Between 612 and 620 nm, the integrated cross section for the acetic acid monomer is (5.23 ± 0.73) × 10(-24) cm(2)·nm·molecule(-1) or (1.38 ± 0.19) × 10(-22) cm(2)·molecule(-1)·cm(-1). This is commensurate with the integrated cross section values for the fourth O-H overtone of other species. Theoretical calculations show that there is sufficient energy for hydrogen to transition between the two oxygen atoms, which results in an overtone-induced conformational change.     

Electronic spectra and photophysics of the α-carboline (1-azacarbazole) monomer

The UV-vis electronic absorption and emission spectra of α-carboline or 1-azacarbazole, 9H-pyrido[2,3-b]indole, AC, have been investigated in aprotic solvents. Radiative, k(r), non-radiative, k(nr), rate constants and natural lifetimes, τ(N), of the AC monomer in hexane and acetonitrile, obtained from the experimentally determined fluorescence quantum yields and fluorescence lifetimes, have been compared with those theoretically estimated. The closeness between these experimental and theoretical data, the small Stokes shifts, the mirror image relationship between the absorption and fluorescence spectra and the close correspondence between the absorption and fluorescence excitation spectra, provide good evidences that the emission of AC monomer occurs directly from its lowest singlet excited state. The mono- and multi-parametric analyses of the AC solvatochromism indicate that the polarity-polarizability, the hydrogen bond donor and the hydrogen bond acceptor properties of the solvent preferentially stabilize the singlet excited over the ground state. These analyses also reveal that photoexcitation reinforces the hydrogen bond donor and acceptor properties of the AC, becoming the pyridinic nitrogen atom more basic and the pyrrolic group more acid.     

Observation and rovibrational analysis of the intermolecular NH3 libration band nu9(1) of H3N-HCN

The high-resolution far-infrared absorption spectrum of the gaseous molecular complex H(3)N-HCN is recorded by means of static gas-phase Fourier transform far-infrared spectroscopy at 247 K, using a synchrotron radiation source. The spectrum contains distinct rotational structures which are assigned to the intermolecular NH(3) libration band nu9(1) (nu(B)) of the pyramidal H(3)N-HCN complex. A rovibrational analysis based on a standard semirigid symmetric top molecule model yields the band origin of 260.03(10) cm(-1), together with values for the upper state rotational constant B' and the upper state quartic centrifugal distortion constants D'(J) and D'(JK). The values for the upper state spectroscopic constants indicate that the hydrogen bond in the H(3)N-HCN complex is destabilized by 5% and elongates by 0.010 A upon excitation of a quantum of libration of the hydrogen bond acceptor molecule.