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A very high accuracy potential energy surface for H3

Wu, Y.-S. Mark and Kuppermann, Aron and Anderson, James B. (1999) A very high accuracy potential energy surface for H3. Physical Chemistry Chemical Physics, 1 (6). pp. 929-937. ISSN 1463-9076. http://resolver.caltech.edu/CaltechAUTHORS:WUYpccp99

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Abstract

An exact quantum Monte Carlo (EQMC) method was used to calculate the potential energy surface (PES) for the ground electronic state of H3 over a grid of about 76000 nuclear geometries. The absolute abinitio statistical or sampling error of the calculation was ±0.01 kcal mol^-1 for energies (V) smaller than 3 eV. This PES was fitted by a three-dimensional cubic spline method and the fitting accuracy was determined from a set of 3684 randomly selected nuclear geometries not used in the fitting. For the range V3 eV the rms fitting error was ±0.010 kcal mol^-1, and the absolute value of the corresponding maximum error was 0.018 kcal mol^-1. This fitted EQMC PES is an order of magnitude more accurate than the best PES previously obtained for this system. Detailed comparisons are made with previous PESs, for the more dynamically important nuclear configurations.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1039/a808797kDOIUNSPECIFIED
http://www.rsc.org/publishing/journals/CP/article.asp?doi=a808797kPublisherUNSPECIFIED
Additional Information:© Royal Society of Chemistry 1999 Received 10th November 1998, Accepted 22nd December 1998 Financial support from NSF Grants No. CHE 9632816 and CHE 9810050 is gratefully acknowledged. The calculations reported were performed on the 512 node Intel Paragon at Caltech's Center for Advanced Computing Research. We thank the sta�ff of the Center for their help. We also thank Dr. Drake L. Diedrich for calculating some points used for an independent verification of the statistical error in the present calculations.
Subject Keywords:INTEGRAL CROSS-SECTIONS; MONTE-CARLO CALCULATION; REACTIVE SCATTERING; GEOMETRIC PHASE; ADIABATIC APPROXIMATION; REACTION H+H2->H2+H; QUANTUM-CHEMISTRY; HYDROGEN MOLECULE; GROUND-STATE; RANDOM-WALK
Record Number:CaltechAUTHORS:WUYpccp99
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:WUYpccp99
Alternative URL:http://dx.doi.org/10.1039/a808797k
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4788
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:06 Sep 2006
Last Modified:26 Dec 2012 09:01

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