What Controls the Quality of Photodynamical Simulations? Electronic Structure Versus Nonadiabatic Algorithm

• Published in: Journal of chemical theory and computation Vol. 19; no. 22; pp. 8273 - 8284
• Main Authors: Janoš, Jiří, Slavíček, Petr
• Format: Journal Article
• Language: English
• Published: Washington American Chemical Society 28.11.2023
• Subjects: Algorithms; Dynamics; Electronic structure; Potential energy; Sensitivity analysis; Wave functions
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.3c00908

The field of nonadiabatic dynamics has matured over the last decade with a range of algorithms and electronic structure methods available at the moment. While the community currently focuses more on developing and benchmarking new nonadiabatic dynamics algorithms, the underlying electronic structure controls the outcome of nonadiabatic simulations. Yet, the electronic-structure sensitivity analysis is typically neglected. In this work, we present a sensitivity analysis of the nonadiabatic dynamics of cyclopropanone to electronic structure methods and nonadiabatic dynamics algorithms. In particular, we compare wave function-based CASSCF, FOMO-CASCI, MS- and XMS-CASPT2, density-functional REKS, and semiempirical MRCI-OM3 electronic structure methods with the Landau–Zener surface hopping, fewest switches surface hopping, and ab initio multiple spawning with informed stochastic selection algorithms. The results clearly demonstrate that the electronic structure choice significantly influences the accuracy of nonadiabatic dynamics for cyclopropanone even when the potential energy surfaces exhibit qualitative and quantitative similarities. Thus, selecting the electronic structure solely on the basis of the mapping of potential energy surfaces can be misleading. Conversely, we observe no discernible differences in the performance of the nonadiabatic dynamics algorithms across the various methods. Based on the above results, we discuss the present-day practice in computational photodynamics.