Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja027963d
Title: Bound state potential energy surface construction: Ab initio zero-point energies and vibrationally averaged rotational constants
Authors: Bettens, R.P.A. 
Issue Date: 15-Jan-2003
Citation: Bettens, R.P.A. (2003-01-15). Bound state potential energy surface construction: Ab initio zero-point energies and vibrationally averaged rotational constants. Journal of the American Chemical Society 125 (2) : 584-587. ScholarBank@NUS Repository. https://doi.org/10.1021/ja027963d
Abstract: Collins' method of interpolating a potential energy surface (PES) from quantum chemical calculations for reactive systems (Jordan, M. J. T.; Thompson, K. C.; Collins, M. A. J. Chem. Phys. 1995, 102, 5647. Thompson, K. C.; Jordan, M. J. T.; Collins, M. A. J. Chem. Phys. 1998, 108, 8302. Bettens, R. P. A.; Collins, M. A. J. Chem. Phys. 1999, 111, 816) has been applied to a bound state problem. The interpolation method has been combined for the first time with quantum diffusion Monte Carlo calculations to obtain an accurate ground state zero-point energy, the vibrationally average rotational constants, and the vibrationally averaged internal coordinates. In particular, the system studied was fluoromethane using a composite method approximating the QCISD(T)/6-311++G(2df,2p) level of theory. The approach adopted in this work (a) is fully automated, (b) is fully ab initio, (c) includes all nine nuclear degrees of freedom, (d) requires no assumption of the functional form of the PES, (e) possesses the full symmetry of the system, (f) does not involve fitting any parameters of any kind, and (g) is generally applicable to any system amenable to quantum chemical calculations and Collins' interpolation method. The calculated zero-point energy agrees to within 0.2% of its current best estimate. A0 and B0 are within 0.9 and 0.3%, respectively, of experiment.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/93212
ISSN: 00027863
DOI: 10.1021/ja027963d
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

13
checked on Sep 17, 2018

WEB OF SCIENCETM
Citations

14
checked on Sep 17, 2018

Page view(s)

27
checked on Aug 10, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.