Far-IR vibration–rotation–tunnelling spectroscopy of the water trimer

Liu, K.; Elrod, Matthew J.; Loeser, J. G.; Cruzan, J. D.; Pugliano, N.; Brown, M. G.; Rzepiela, Jeffrey A.; Saykally, Richard J.

doi:10.1039/fd9949700035

Cited by 70 publications

(59 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2 for ͑H 2 O͒ 3 and in Table III and Fig. 3 for ͑D 2 O͒ 3 . In order to investigate the effect of the three-body interactions, we performed the calculations with the CC-pol potential at three different levels: ͑i͒ with the potential as a sum of pair interactions only, labeled CC-pol͑2B͒; ͑ii͒ with the three-body polarization ͑or induction͒ energy added that is included in the polarizable CC-pol potential, labeled CC-pol; and ͑iii͒ with the full three-body interaction added that includes also the nonadditive exchange interactions, labeled CC-pol+ 3B.…”

Section: Resultsmentioning

confidence: 99%

“…They also led to an effective rotation-tunneling Hamiltonian that was used successfully to interpret and extract physically meaningful parameters from the measured high-resolution spectra. 4,5 A fourdimensional ab initio potential involving the torsional degrees of freedom and the symmetric hydrogen-bond stretch mode was computed by Sabo et al, [8][9][10] who used this potential in a four-dimensional dynamics calculation and investigated the effect of torsional and stretch excitations on the rotational constants of ͑H 2 O͒ 3 and ͑D 2 O͒ 3 .…”

Section: Theorymentioning

confidence: 99%

“…For the ͑vibrationally averaged͒ trimer rotational constants we took the values A = B = 0.221 72 cm −1 and C = 0.110 86 cm −1 determined experimentally 4 for the ground state of ͑H 2 O͒ 3 . For ͑D 2 O͒ 3 we took the experimental 5 …”

Section: Calculationsmentioning

confidence: 99%

“…1 Since then, a number of torsional bands of ͑H 2 O͒ 3 and ͑D 2 O͒ 3 have been added 2-5 to the first observation, which completely determine the torsional levels of these two isotopomers up to energies of about 150 and 100 cm −1 , respectively. Many calculations have been performed on ͑H 2 O͒ 3 , ͑D 2 O͒ 3 , and the mixed isotope forms of the water trimer in order to theoretically describe this manifold of states. In most cases semiempirical potentials were used in these calculations or, when ab initio potentials were applied, they were specifically calculated for the restricted dimensionality model used in the computation of the torsional levels.…”

Section: Introductionmentioning

confidence: 99%

“…In most cases semiempirical potentials were used in these calculations or, when ab initio potentials were applied, they were specifically calculated for the restricted dimensionality model used in the computation of the torsional levels. In a few of the papers 6,14,21 the trimer levels of ͑H 2 O͒ 3 and ͑D 2 O͒ 3 were used to test a global ab initio water force field including pair and three-body interactions. Reference 25 reviews the work up to the year 2000.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

Avoird

Szalewicz

2008

The Journal of Chemical Physics

View full text Add to dashboard Cite

The torsional levels of ͑H 2 O͒ 3 and ͑D 2 O͒ 3 were calculated in a restricted dimensionality ͑three-dimensional͒ model with several recently proposed water potentials. Comparison with the experimental data provides a critical test, not only of the pair interactions that have already been probed on the water dimer spectra, but also of the nonadditive three-body contributions to the potential. The purely ab initio CC-pol and HBB potentials that were previously shown to yield very accurate water dimer levels, also reproduce the trimer levels well when supplemented with an appropriate three-body interaction potential. The TTM2.1 potential gives considerably less good agreement with experiment. Also the semiempirical VRT͑ASP-W͒III potential, fitted to the water dimer vibration-rotation-tunneling levels, gives substantial disagreement with the measured water trimer levels, which shows that the latter probe the potential for geometries other than those probed by the dimer spectrum. Although the three-body nonadditive interactions significantly increase the stability of the water trimer, their effect on the torsional energy barriers and vibration-tunneling frequencies is less significant.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

Avoird

Szalewicz

2008

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

Torsional eigenvalues of the water trimer on several ab initio potential surfaces

Guiang

Wyatt

1998

Int. J. Quant. Chem.

View full text Add to dashboard Cite

Eigenvalues corresponding to the three torsional degrees of freedom were calculated for the water trimer and its deuterated isotopomer in four sets of calculations involving different potential energy surfaces. The four potential surfaces were developed in this work by reparametrization of the CKL function against four sets of ab initio energies calculated with and without counterpoise correction. Transition frequencies corresponding to the low-frequency torsional motions of the trimer were calculated and then compared with those found from experiment to assess the accuracy of each potential energy surface. Although reparametrization of the CKL function to a set of counterpoise-corrected energies yielded transition energies that are in qualitative agreement with those from experiment, reparametrization to another set of counterpoise-corrected energies resulted in highly inaccurate values of the transition energy. As a consequence, our results demonstrate that caution must be exercised in the implementation of the counterpoise method as it does not always lead to more accurate ab initio calculations.

show abstract

High‐ResolutionFTIRand Diode Laser Spectroscopy of Supersonic Jets

Snels

Horká‐Zelenková

Hollenstein

et al. 2011

Handbook of High‐resolution Spectroscopy

View full text Add to dashboard Cite

Fourier transform infrared (FTIR) spectrometers and tunable diode lasers in combination with a supersonic molecular beam expansion are a perfect tool for the investigation of molecules, ions, and radicals at low temperatures. The internal degrees of freedom of the molecules are adiabatically cooled to very low temperatures and thus only low-lying energy levels are populated. The reduction of the number of populated levels at low temperatures makes the assignment of the spectra much easier as compared to the congested room-temperature spectra. Under certain conditions, the Doppler linewidths are greatly reduced, corresponding to very low effective translational temperatures. Supersonic expansion also provides a suitable method for producing and investigating van der Waals clusters and hydrogen-bonded complexes. Unstable species such as radicals and ions can be efficiently produced and studied in a molecular beam. The low rotational temperature allows for the study of nuclear spin symmetry conservation or conversion between nuclear spin isomers. A molecular beam expansion can be obtained by expanding gas through a slit or a circular nozzle. Both expansion geometries can be used in combination with a multipass optical setup and with cavity ring down spectroscopy, which enhances the effective absorption path length. Cooling of the molecules can be promoted by seeding in noble gases. This article summarizes the general aspects of the experimental technique as well as current developments. To demonstrate how powerful the combination of a molecular beam expansion with tunable diode laser and FTIR spectroscopy can be, we report results on some important current examples.

show abstract

Far-IR vibration–rotation–tunnelling spectroscopy of the water trimer

Cited by 70 publications

References 21 publications

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

Torsional eigenvalues of the water trimer on several ab initio potential surfaces

High‐ResolutionFTIRand Diode Laser Spectroscopy of Supersonic Jets

Contact Info

Product

Resources

About