TY - JOUR

T1 - Improved dual-level direct dynamics method for reaction rate calculations with inclusion of multidimensional tunneling effects and validation for the reaction of H with trans-N2H2

AU - Chuang, Yao Yuan

AU - Truhlar, Donald G

PY - 1997/5/15

Y1 - 1997/5/15

N2 - A new scheme for carrying out dual-level direct dynamics calculations is presented in this paper. A better estimate of the barrier width is obtained by using the high-level imaginary frequency at the saddle point as well as high-level values of the energies of three stationary points (i.e., reactants, products, and saddle point). Furthermore, a more robust formula is introduced for incorporating high-level vibrational frequency corrections on the generalized normal modes along the reaction path. Incorporating these improvements, we carry out dual-level calculations of the reaction rate of H + N2H2 → H2 + N2H by employing variational transition-state theory with optimized multidimensional tunneling. Dual-level calculations at the level of zero-curvature tunneling (ZCT) show excellent agreement with an earlier calculation involving high-level computations at 11 times as many geometries. Having validated the dual-level approach at the ZCT level, we next extend the dual-level calculations to include small-curvature, large-curvature, and optimized multidimensional tunneling approximations. Four choices of low-level surface are used to gauge the sensitivity to these choices.

AB - A new scheme for carrying out dual-level direct dynamics calculations is presented in this paper. A better estimate of the barrier width is obtained by using the high-level imaginary frequency at the saddle point as well as high-level values of the energies of three stationary points (i.e., reactants, products, and saddle point). Furthermore, a more robust formula is introduced for incorporating high-level vibrational frequency corrections on the generalized normal modes along the reaction path. Incorporating these improvements, we carry out dual-level calculations of the reaction rate of H + N2H2 → H2 + N2H by employing variational transition-state theory with optimized multidimensional tunneling. Dual-level calculations at the level of zero-curvature tunneling (ZCT) show excellent agreement with an earlier calculation involving high-level computations at 11 times as many geometries. Having validated the dual-level approach at the ZCT level, we next extend the dual-level calculations to include small-curvature, large-curvature, and optimized multidimensional tunneling approximations. Four choices of low-level surface are used to gauge the sensitivity to these choices.

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M3 - Article

AN - SCOPUS:0000785899

VL - 101

SP - 3808

EP - 3814

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 20

ER -