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Data for Assessing and rationalizing the performance of Hessian update schemes for reaction path Hamiltonian rate calculations Raphael Chantreau Majerus (24958372) Christopher Robertson (6095033) Scott Habershon (1263891) Chemical kinetics -- Mathematical models Chemical reactions -- Mathematical models Molecular theory, Chemistry Physical and theoretical -- Data processing Statistical mechanics Migrated from ePrints The reaction path Hamiltonian (RPH) can be used to calculate chemical reaction rate constants, going beyond transition-state theory in taking account of recrossing by providing an approximation to the dynamic transmission coefficient. However, the RPH necessitates the calculation of the Hessian matrix at a number of points along the input minimum energy path; the associated computational cost stands as a bottleneck in RPH calculations, especially if one is interested in using high-accuracy electronic structure methods. In this work, three different Hessian update schemes (symmetric rank-1, Powell-symmetric Broyden, and Bofill updates) are assessed to see whether or not they reliably reproduce calculated transmission coefficients for three different chemical reactions. The symmetric rank-1 scheme and the Powell-symmetric Broyden scheme both resulted in the most reliable and accurate Hessian update methods, with transmission coefficients which were in good agreement with those calculated by the standard RPH calculations using analytical Hessian matrices. The relative accuracy of the different Hessian update schemes is further rationalized by investigating the approximated coriolis and curvature coupling terms along the reaction-path, providing insight into when these schemes woould be expected to work well. Furthermore, the associated computational cost associated with the RPH calculations was substantially reduced by the tested update schemes. Together, these results provide useful rules-of-thumb for using Hessian update schemes in RPH simulations.<br><br>Figure_2_a.dat contains the data for Figure 2 Figure_2_b.dat contains the data for Figure 2 Figure_4_a.dat contains the data for Figure 4 Figure_4_b.dat contains the data for Figure 4 Figure_6_a.dat contains the data for Figure 6 Figure_6_b.dat contains the data for Figure 6 Figure_7_a.dat contains the data for Figure 7 part a Figure_7_b.dat contains the data for Figure 7 part b Figure_7_c.dat contains the data for Figure 7 part c Figure_8_a.dat contains the data for Figure 8 part a Figure_8_b.dat contains the data for Figure 8 part b Figure_8_c.dat contains the data for Figure 8 part c Figure_9.dat contains the data for Figure 9 Figure_10_a.dat contains the data for Figure 10 part a Figure_10_b.dat contains the data for Figure 10 part b Figure_10_c.dat contains the data for Figure 10 part c Figure_10_d.dat contains the data for Figure 10 part d 2022-02-02T00:00:00Z Dataset Dataset 10.82444/warw.33825406.v1 https://figshare.com/articles/dataset/Data_for_Assessing_and_rationalizing_the_performance_of_Hessian_update_schemes_for_reaction_path_Hamiltonian_rate_calculations/33825406 CC BY 4.0