{"title":"仅使用反应物雅可比坐标求解坐标问题:一种新的量子波包方法用于生成物状态分辨反应散射计算。","authors":"Weijie Du, and , Zhigang Sun*, ","doi":"10.1021/acs.jctc.5c01052","DOIUrl":null,"url":null,"abstract":"<p >In the traditional concept, the Jacobi coordinates of the reactants cannot be efficient for calculating product state-resolved information of a reactive scattering process with a quantum wave packet method. This so-called coordinate problem is cracked in this work but by using only the reactant Jacobi coordinate. In the proposed method, the grid points in all three degrees of freedom (including the angular one using the Lagrange interpolation polynomials method) are optimally selected according to the shape of the potential energy surface (PES), so only the necessary grid points (the smallest number of grid points) within the range need to be retained in the calculations. Therefore, the numerical efficiency of the method is comparable to the most efficient ones with the domain decomposition technique or domain decoupling technique, where the optimized coordinates are used in each domain, such as the previous interaction-asymptotic region decomposition (IARD) method, especially when a long-range interaction potential is involved in the calculations. The reaction between <i>F</i> and <i>H</i><sub>2</sub> with <i>J</i> = 0, which involves long-range resonance states and some states of product with extremely slow translational energy, thus requiring a huge grid range in the calculation, is taken as the numerical example to demonstrate the numerical performance and efficiency of the proposed method. This method is uniformly stable, unlike the previous IARD method, and is expected to be very attractive in a reactive scattering calculation for reactions involving a long-range interaction potential.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"21 19","pages":"9259–9269"},"PeriodicalIF":5.5000,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Coordinate Problem Cracking by Using Only the Reactant Jacobi Coordinates: A New Quantum Wave Packet Method for Product State-Resolved Reactive Scattering Calculations\",\"authors\":\"Weijie Du, and , Zhigang Sun*, \",\"doi\":\"10.1021/acs.jctc.5c01052\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In the traditional concept, the Jacobi coordinates of the reactants cannot be efficient for calculating product state-resolved information of a reactive scattering process with a quantum wave packet method. This so-called coordinate problem is cracked in this work but by using only the reactant Jacobi coordinate. In the proposed method, the grid points in all three degrees of freedom (including the angular one using the Lagrange interpolation polynomials method) are optimally selected according to the shape of the potential energy surface (PES), so only the necessary grid points (the smallest number of grid points) within the range need to be retained in the calculations. Therefore, the numerical efficiency of the method is comparable to the most efficient ones with the domain decomposition technique or domain decoupling technique, where the optimized coordinates are used in each domain, such as the previous interaction-asymptotic region decomposition (IARD) method, especially when a long-range interaction potential is involved in the calculations. The reaction between <i>F</i> and <i>H</i><sub>2</sub> with <i>J</i> = 0, which involves long-range resonance states and some states of product with extremely slow translational energy, thus requiring a huge grid range in the calculation, is taken as the numerical example to demonstrate the numerical performance and efficiency of the proposed method. This method is uniformly stable, unlike the previous IARD method, and is expected to be very attractive in a reactive scattering calculation for reactions involving a long-range interaction potential.</p>\",\"PeriodicalId\":45,\"journal\":{\"name\":\"Journal of Chemical Theory and Computation\",\"volume\":\"21 19\",\"pages\":\"9259–9269\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-09-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Theory and Computation\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jctc.5c01052\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jctc.5c01052","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Coordinate Problem Cracking by Using Only the Reactant Jacobi Coordinates: A New Quantum Wave Packet Method for Product State-Resolved Reactive Scattering Calculations
In the traditional concept, the Jacobi coordinates of the reactants cannot be efficient for calculating product state-resolved information of a reactive scattering process with a quantum wave packet method. This so-called coordinate problem is cracked in this work but by using only the reactant Jacobi coordinate. In the proposed method, the grid points in all three degrees of freedom (including the angular one using the Lagrange interpolation polynomials method) are optimally selected according to the shape of the potential energy surface (PES), so only the necessary grid points (the smallest number of grid points) within the range need to be retained in the calculations. Therefore, the numerical efficiency of the method is comparable to the most efficient ones with the domain decomposition technique or domain decoupling technique, where the optimized coordinates are used in each domain, such as the previous interaction-asymptotic region decomposition (IARD) method, especially when a long-range interaction potential is involved in the calculations. The reaction between F and H2 with J = 0, which involves long-range resonance states and some states of product with extremely slow translational energy, thus requiring a huge grid range in the calculation, is taken as the numerical example to demonstrate the numerical performance and efficiency of the proposed method. This method is uniformly stable, unlike the previous IARD method, and is expected to be very attractive in a reactive scattering calculation for reactions involving a long-range interaction potential.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.