TY - JOUR
T1 - Plumbing Potentials for Molecules with up to Tens of Atoms
T2 - How to Find Saddle Points and Fix Leaky Holes
AU - Pandey, Ankit
AU - Poirier, Bill
N1 - Funding Information:
This work was largely supported by a grant from The Robert A. Welch Foundation (D-1523). In addition, both a research grant (CHE-1665370) and a CRIF MU instrumentation grant (CHE-0840493) from the National Science Foundation are acknowledged. The authors also gratefully acknowledge the Texas Tech University High Performance Computing Center for providing access and technical support to their Quanah computing cluster facility. This article is dedicated to the memory of Prof. William L. Hase.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/8/6
Y1 - 2020/8/6
N2 - Potential energy surfaces (PESs) play an indispensable role in molecular dynamics but are notoriously difficult to flesh out properly in large-dimensional spaces. In particular, the undetected presence of PES holes, i.e., unphysical saddle points beyond which the potential energy drops arbitrarily, can have devastating effects on both classical and quantum dynamics calculations. In this study, the Crystal algorithm is developed as a tool for efficiently and accurately finding PES holes, as well as legitimate saddle points, even in very large-dimensional configuration spaces. The approach is applied to three large-dimensional PESs for molecular systems of current interest: Uracil, naphthalene, and formic acid dimer. Low-lying PES holes are discovered and located for the first two systems-including naphthalene, for which no holes were previously suspected, to the best of our knowledge. Likewise, the double-well, double-proton-transfer isomerization saddle point for formic acid dimer is also located.
AB - Potential energy surfaces (PESs) play an indispensable role in molecular dynamics but are notoriously difficult to flesh out properly in large-dimensional spaces. In particular, the undetected presence of PES holes, i.e., unphysical saddle points beyond which the potential energy drops arbitrarily, can have devastating effects on both classical and quantum dynamics calculations. In this study, the Crystal algorithm is developed as a tool for efficiently and accurately finding PES holes, as well as legitimate saddle points, even in very large-dimensional configuration spaces. The approach is applied to three large-dimensional PESs for molecular systems of current interest: Uracil, naphthalene, and formic acid dimer. Low-lying PES holes are discovered and located for the first two systems-including naphthalene, for which no holes were previously suspected, to the best of our knowledge. Likewise, the double-well, double-proton-transfer isomerization saddle point for formic acid dimer is also located.
UR - http://www.scopus.com/inward/record.url?scp=85089616016&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.0c01435
DO - 10.1021/acs.jpclett.0c01435
M3 - Article
C2 - 32687368
AN - SCOPUS:85089616016
VL - 11
SP - 6468
EP - 6474
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 15
ER -