Tunable far-infrared laser spectroscopy of deuterated isotopomers of Ar–H2O

Suzuki, Sayaka; Bumgarner, Roger E.; Stockman, Paul A.; Green, Peter G.; Blake, Geoffrey A.

doi:10.1063/1.460308

Cited by 52 publications

(24 citation statements)

References 14 publications

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“…The water-methanol dimer is the latest, and one of the most chemically complex, in a series of water-containing, hydrogen-bonded dimers studied in our laboratories by microwave and far-infrared spectroscopy, for the purpose of fitting the observed spectra to intermolecular potential energy surfaces ͑IPSs͒. [1][2][3][4][5][6][7][8][9][10][11] The complex formed between methanol and water is particularly interesting because both hydrophobic and hydrophilic forces contribute strongly to the IPS of this relatively small dimer, creating a high degree of anisotropy. In addition, the watermethanol dimer will provide a test of the adaptability of the IPSs of simpler dimers to larger, multi-functional interactions.…”

Section: Introductionmentioning

confidence: 99%

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Stockman

Blake

Lovas

et al. 1997

The Journal of Chemical Physics

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O between 7 and 24 GHz using a Fourier-transform microwave spectrometer. Because CH 3 OH and H 2 O are capable of both accepting and donating hydrogen bonds, there exists some question as to which donor-acceptor pairing of the molecules is the lowest energy form. This question is further emphasized by the ambiguity and variety present in previous experimental and computational results. Transitions arising from the methyl torsional A state were assigned in each of the studied isotopomers, and for the A and E states in , where the errors correspond to 1 uncertainties-are consistent with either conformation, the fit of the structure to the rotational constants demonstrates unambiguously that the lower-energy conformation formed in supersonically cooled molecular beams corresponds to a water-donor, methanol-acceptor complex. The results and implications for future work are also discussed in terms of the permutation-inversion theory presented by Hougen and Ohashi ͓J. Mol. Spectros. 159, 363 ͑1993͔͒.

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Section: Introductionmentioning

confidence: 99%

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Stockman

Blake

Lovas

et al. 1997

The Journal of Chemical Physics

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“…The shift in the Ar-HOD vibrational origin from the HOD monomer origin is assumed to have the same value as the corresponding shift in the Ar-H 2 O system, i.e., 3.12 cm Ϫ1 . 12 Blake and co-workers 25 have measured the energy of the ⌸(1 01 ) state with respect to the lowest ⌺(0 00 ) in ArϪHOD in the far IR to be 19.90 cm Ϫ1 . The corresponding energy splitting between the ⌺(1 01 ) and ⌸(1 01 ) states, however, has not been measured experimentally but has been calculated using the Ar-H 2 O potential energy surface 13 to be 10.89 cm Ϫ1 .…”

Section: A Overtone Spectroscopy Of the Ar-hod Complexmentioning

confidence: 98%

“…The corresponding energy splitting between the ⌺(1 01 ) and ⌸(1 01 ) states, however, has not been measured experimentally but has been calculated using the Ar-H 2 O potential energy surface 13 to be 10.89 cm Ϫ1 . 25 In predicting the position of the Ar-HOD band it was assumed that the rotational spacings are the same for v OH ϭ0 and v OH ϭ3 vibrational states of Ar-HOD.…”

Section: A Overtone Spectroscopy Of the Ar-hod Complexmentioning

confidence: 99%

Intracluster stereochemistry in van der Waals complexes: Steric effects in ultraviolet photodissociation of state-selected Ar–HOD/H2O

Votava

Mackenzie

Nesbitt

2004

The Journal of Chemical Physics

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High-resolution IR-UV multiple resonance methods are employed to elucidate the photodissociation dynamics of quantum state-selected Ar-HOD and Ar-H(2)O van der Waals clusters. A single mode pulsed OPO operating in the region of the OH second overtone is used to prepare individual rovibrational states that are selectively photodissociated at specific excimer wavelengths. Subsequent fluorescence excitation of the resulting OH (OD) fragments yields dynamical information on the photofragmentation event and any resulting intracluster collisions. This technique is used to characterize spectroscopically the Pi(1(01)), nu(OH)=3<--Sigma(0(00)), v(OH)=0 overtone band of the Ar-HOD complex with an origin at 10648.27 cm(-1). The effects of Ar complexation on the dissociation dynamics are inferred by comparison of the OD photofragment quantum state distributions resulting from dissociation of single rovibrational states of the complex with those from isolated HOD photodissociation. The important role played by the initial internal state of the complex is demonstrated by comparison of the current Ar-HOD data with previously published results for the Ar-H(2)O Sigma(0(00))[03(-)> state. We interpret the dramatic differences in the dynamics of the two systems as manifestations of the nodal structure of the vibrational state in the parent complex and the way in which it governs the collision probability between the Ar atom and the escaping photofragments.

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“…The inversion-tunneling of NH3 was originally included by a simple two-state model, but presently we have extended our formalism and computer codes with a basis for the NH3 umbrella coordinate, so that we can include explicitly the U2 vibration and the inversion-tunneling of the NH3 monomer in the Ar-NH3 complex. The results are extensively described in recent papers by Van Bladel et al [86,87] and compared in detail with experimental d ata [78][79][80][81][82][83][84][85], Since the topic of Van der Waals molecules will be covered in this workshop by Hutson and by Brechignac, I have limited myself here to a summary of the main conclusions. It has been found that, indeed, the spectra of these Van der W aals complexes are extremely sensitive to the shape of the potential surface in the entire attractive region.…”

Section: Experim Ent Spherical Expansionmentioning

confidence: 99%

“…(1 1 ), we have applied them to the calculation of the microwave and farinfrared spectra of Ar-NH3 [67,[78][79][80][81][82], Ar-H^O [83,84] and A r-D 20 [82,85]. For the latter system we had first to transform the Ar-TI20 potential to a different center of mass.…”

Section: Spectra Op Van Der Waals Moleculesmentioning

confidence: 99%

Overview on Intermolecular Potentials

Avoird

1992

Status and Future Developments in the Study of Transport Properties

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In trod u ctionAs will be substantiated in this workshop, the knowledge of intermolecular potentials opens the way to (the calculation of) many observable properties, for microscopic as well as macroscopic systems. In the first category are thermodynamic stability, the spectra of Van der Waals molecules [1][2][3][4], an d molecular beam scattering cross sections [5][6][7], elastic or inelastic state-to-state, to tal or differential. In the second category are various bulk gas and condensed m atter properties. Measured gas phase properties [8,9] which depend directly on the intermolecular potential are virial coef ficients, viscosity and diffusion coefficients, therm al conductivity, sound absorption, pressure broadening of spectral lines, nuclear m agnetic relaxation and depolarized Rayleigh scattering. Additional information is obtained from the effects of electric and magnetic fields on the transport properties (Senftleben-Beenakker effects). 2stability and lattice vibrations of molecular solids [11]. On the other hand, all the measured data may be used, and have actually been used in several examples, to construct or improve (semi-)empirical intermolecular potentials.Several reviews on intermolecular potentials have appeared during the past five years [2,3,[12][13][14][15][16], and hence I shall simply outline the most important points. In teractions between molecules are usually divided into long-range interactions and short-range interactions. At long range, i.e. when the charge clouds of the interacting molecules do not overlap, the interaction energy can be obtained formally by standard Rayleigh-Schrödinger perturbation theory. The perturbation, which is the intermolecular interaction operator, can be expanded as a multipole series in powers of R~1, where R is the distance between th e centers-of-mass of the molecules. The first-order energy is the electrostatic multipole-multipole interaction energy. The second-order energy contains the induction (multipole-induced multipole) energy and the (nonclassical) dispersion energy. For molecular ions the electrostatic and induction in teractions are strongly dominant. For polar, e.g. hydrogen bonded, molecules the electrostatic interactions are still the most important contribution, while the induc tion and dispersion energies are comparable. For apolar molecules, i.e. molecules with small dipole moments, the dispersion energy becomes the most important (attractive) long range interaction. The long range interactions are completely determined by the permanent multipole moments and the, static as well as frequency-dependent, multi pole polarizabilities of the monomers.Since the molecular charge clouds have exponential tails, there is always some overlap between them. The effects of this overlap are twofold. Penetration causes the exact electrostatic interaction between continuous, overlapping charge clouds to deviate from its representation by a multipole series. This is correctly included in the Rayleigh-Schrodinger perturbation theory if one avoids the expansi...

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Tunable far-infrared laser spectroscopy of deuterated isotopomers of Ar–H2O

Cited by 52 publications

References 14 publications

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Microwave rotation-tunneling spectroscopy of the water–methanol dimer: Direct structural proof for the strongest bound conformation

Intracluster stereochemistry in van der Waals complexes: Steric effects in ultraviolet photodissociation of state-selected Ar–HOD/H2O

Overview on Intermolecular Potentials

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