Superfluid response of 4HeN–N2O clusters probed by path integral Monte Carlo simulations

Wang, Lecheng; Xie, Daiqian; Guo, Hua; Li, Hui; Roy, Robert J. Le; Roy, Pierre‐Nicholas

doi:10.1016/j.jms.2011.03.007

Cited by 15 publications

(13 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 3 shows that there is a monotonic and almost linear increase in the band origin shifts below N = 5, which can be attributed to the formation of the five-membered donut ring. 19 This configuration is a consequence of the deep Tshaped potential minimum of the dimer potential. A sharp turnaround takes place between N = 5 and 6, due to occupancy at the oxygen side by additional heliums as presented in our previous work.…”

Section: B Vibrational Band Origin Shift For the N 2 O−he N Clustersmentioning

confidence: 94%

“…A sharp turnaround takes place between N = 5 and 6, due to occupancy at the oxygen side by additional heliums as presented in our previous work. 19 Afterwards, v N decreases with N until N > 17, when the calculated band origin shift levels off. In the large cluster limit, the behavior of our predicted shift is consistent with experimental observation.…”

Section: B Vibrational Band Origin Shift For the N 2 O−he N Clustersmentioning

confidence: 96%

“…18 Recently, we constructed a new three-dimensional (3D) PES with an aug-cc-PVQZ basis set by involving the Q 3 mode of N 2 O with other internal modes fixed at their averaged values of the corresponding vibrational state. 19 The path integral Monte Carlo (PIMC) simulations based on this PES reproduced the rotational constants accurately. However, the prediction of the shift of the vibrational band origin was not satisfactory.…”

Section: Introductionmentioning

confidence: 91%

“…[15][16][17][18][19] Earlier theoretical studies for the rovibrational spectra of the N 2 O−He complex were performed based on two-dimensional (2D) N 2 O−He PESs with fixed internal modes of N 2 O. [15][16][17] While a 2D treatment may be adequate for describing the rotational spectra, it could not properly describe infrared spectra involving excitation of an intramolecular N 2 O vibrational mode.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A new four-dimensional ab initio potential energy surface for N2O–He and vibrational band origin shifts for the N2O–HeN clusters with N = 1–40

Wang

Xie

Roy

et al. 2012

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

A new four-dimensional ab initio potential energy surface for N(2)O-He is constructed at the CCSD(T) level with an aug-cc-pVQZ basis set together with bond functions. The vibrational coordinates Q(1) and Q(3) of N(2)O are explicitly included, due to the strong coupling between the symmetric and asymmetric stretches of N(2)O. A global potential energy surface is obtained by fitting the original potential points to a four-dimensional Morse∕long range (MLR) analytical form. In the fitting, the ab initio noise in the long range region of the potential is smoothed over by theoretically fixed long range parameters. Two-dimensional intermolecular potentials for both the ground and the excited υ(3) states of N(2)O are then constructed by vibrationally averaging the four-dimensional potential. Based on the two-dimensional potentials, we use the path integral Monte Carlo algorithm to calculate the vibrational band origin shifts for the N(2)O-He(N) clusters using a first order perturbation theory estimate. The calculated shifts agree reasonably well with the experimental values and reproduce the evolution tendency from dimer to large clusters.

show abstract

Section: B Vibrational Band Origin Shift For the N 2 O−he N Clustersmentioning

confidence: 94%

Section: B Vibrational Band Origin Shift For the N 2 O−he N Clustersmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A new four-dimensional ab initio potential energy surface for N2O–He and vibrational band origin shifts for the N2O–HeN clusters with N = 1–40

Wang

Xie

Roy

et al. 2012

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] These in turn stimulated considerable theoretical work on determining accurate chromophore-He interaction potentials and on simulating the properties of these chromophore-He n species. [19][20][21][22][23][24][25][26][27][28][29][30] Carbonyl sulfide (OCS) is a favorite probe molecule for experimental helium cluster studies, because it is a strong chromophore in both the microwave and infrared regions, and its rotational constant B is neither too large nor small. High resolution microwave and infrared spectra of (He) N -OCS clusters with N from 1 up to 8 have been first measured in 2002 by Tang et.…”

Section: Introductionmentioning

confidence: 99%

An intramolecular vibrationally excited intermolecular potential for He–OCS: Globally tested by simulation of vibrational shifts for OCS in HeN N = 1 − 100 Clusters

2012

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

An effective four-dimensional ab initio potential energy surface (PES) for He-OCS, which explicitly incorporates dependence on the intramolecular Q(1) (O-C) stretch normal mode of OCS and is parametrically dependent on its Q(3) (C-S) stretch coordinate has been calculated at the coupled-cluster single double triple/aug-cc-pVQZ level including bond functions. Analytic two-dimensional PESs are obtained by least-squares fitting vibrationally averaged interaction energies for v(1)(OCS)= 0, and 1 to the Morse/long-range potential function form. These fits to 305 points both have root-mean-square (rms) deviation of 0.022 cm(-1), and require only 49 parameters. The resulting vibrationally averaged PESs provide good representations of the experimental microwave and infrared data: for 10 microwave transitions, and 51 infrared transitions of the He-OCS dimer, the rms discrepancies are only 93.2 MHz and 0.003 cm(-1), respectively, which are more than four times better than previous theoretical predictions on their original ab initio potentials. The calculated infrared band origin shift associated with the v(1) fundamental of OCS is blueshifted by 0.082 cm(-1) for He-OCS dimer, which is in good agreement with the experimental value of 0.111 cm(-1). The path integral Monte Carlo algorithm and a first order perturbation theory estimate are used to simulate the ν(1) vibrational band origin frequency shifts of OCS in He(n) clusters for N = 1 - 100 . The predicted vibrational frequency shifts with first a blueshift for small N and then followed by a transition to a redshift for larger N are in excellent agreement with experiment across the whole range of N. These results for increasing N demonstrate the high quality of these potentials and globally test the accuracy not only the near global minimum, but also in regions not accessed by N = 1 He-OCS dimer.

show abstract

Reactive path integral quantum simulations of molecules solvated in superfluid helium

Walewski

Forbert

Marx

2014

Computer Physics Communications

View full text Add to dashboard Cite

Superfluid response of 4HeN–N2O clusters probed by path integral Monte Carlo simulations

Cited by 15 publications

References 60 publications

A new four-dimensional ab initio potential energy surface for N2O–He and vibrational band origin shifts for the N2O–HeN clusters with N = 1–40

A new four-dimensional ab initio potential energy surface for N2O–He and vibrational band origin shifts for the N2O–HeN clusters with N = 1–40

An intramolecular vibrationally excited intermolecular potential for He–OCS: Globally tested by simulation of vibrational shifts for OCS in HeN N = 1 − 100 Clusters

Reactive path integral quantum simulations of molecules solvated in superfluid helium

Contact Info

Product

Resources

About