arXiv - PHYS - Chemical Physics最新文献_第3页

Advanced perturbation scheme for efficient polarizability computations 用于高效极化计算的先进扰动方案

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-16 DOI: arxiv-2409.10184

Anoop Ajaya Kumar Nair, Julian Bessner, Timo Jacob, Elvar Örn Jónsson

{"title":"Advanced perturbation scheme for efficient polarizability computations","authors":"Anoop Ajaya Kumar Nair, Julian Bessner, Timo Jacob, Elvar Örn Jónsson","doi":"arxiv-2409.10184","DOIUrl":"https://doi.org/arxiv-2409.10184","url":null,"abstract":"We present an efficient momentum based perturbation scheme to evaluate\u0000polarizability tensors of small molecules and at the fraction of the\u0000computational cost compared to conventional energy based perturbation schemes.\u0000Furthermore, the simplicity of the scheme allows for the seamless integration\u0000into modern quantum chemistry codes. We apply the method to systems where the\u0000wavefunctions are described on a real-space grid and are therefore not subject\u0000to finite size basis set errors. In the grid-based scheme errors can be\u0000attributed to the resolution and the size of the grid-space. The applicability\u0000and generality of the method is exhibited by calculating polarizability tensors\u0000including the dipole-dipole and up to the quadrupole-quadrupole for a series of\u0000small molecules, representing the most common symmetry groups. By a direct\u0000comparison with standard techniques based on energy perturbation we show that\u0000the method reduces the number of explicit computations by a factor of 30.\u0000Numerical errors introduced due to the arrangement of the explicit point\u0000charges are eliminated with an extrapolation scheme to the effective\u0000zero-perturbation limit.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142269163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accurate experimental ($p$, $ρ$, $T$) data of natural gas mixtures for the assessment of reference equations of state when dealing with hydrogen-enriched natural gas 天然气混合物的精确实验（$p$、$ρ$、$T$）数据，用于评估处理富氢天然气时的参考状态方程

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-15 DOI: arxiv-2409.09672

Roberto Hernández-Gómez, Dirk Tuma, Daniel Lozano-Martín, César R. Chamorro

{"title":"Accurate experimental ($p$, $ρ$, $T$) data of natural gas mixtures for the assessment of reference equations of state when dealing with hydrogen-enriched natural gas","authors":"Roberto Hernández-Gómez, Dirk Tuma, Daniel Lozano-Martín, César R. Chamorro","doi":"arxiv-2409.09672","DOIUrl":"https://doi.org/arxiv-2409.09672","url":null,"abstract":"The GERG-2008 equation of state is the approved ISO standard (ISO 20765-2)\u0000for the calculation of thermophysical properties of natural gas mixtures. The\u0000composition of natural gas can vary considerably due to the diversity of\u0000origin. Further diversification was generated by adding hydrogen, biogas, or\u0000other non-conventional energy gases. In this work, high-precision experimental\u0000($p$, $rho$, $T$) data for two gravimetrically prepared synthetic natural gas\u0000mixtures are reported. One mixture resembled a conventional natural gas of 11\u0000components (11 M) with a nominal mixture composition (amount-of-substance\u0000fraction) of 0.8845 for methane as the matrix compound. The other mixture was a\u000013-component hydrogen-enriched natural gas with a low calorific value featuring\u0000a nominal composition of 0.7885 for methane. Density measurements were\u0000performed in an isothermal operational mode at temperatures between 260 and 350\u0000K and at pressures up to 20 MPa by using a single-sinker densimeter with\u0000magnetic suspension coupling. The data were compared with the corresponding\u0000densities calculated from both GERG-2008 and AGA8-DC92 equations of state to\u0000test their performance on real mixtures. The average absolute deviation from\u0000GERG-2008 (AGA8-DC92) is 0.027% (0.078%) for 11 M and 0.095% (0.062%) for the\u000013-component $H_{2}$-enriched mixture, respectively. The corresponding maximum\u0000relative deviation from GERG-2008 (AGA8-DC92) amounts to 0.095% (0.127%) for 11\u0000M and 0.291% (0.193%) for the $H_{2}$-enriched mixture.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Resonant molecular transitions in second harmonic generation spectroscopy of Fe-octaethylporphyrin adsorbed on Cu(001) 吸附在铜(001)上的八乙基卟啉的二次谐波发生光谱中的共振分子跃迁

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-15 DOI: arxiv-2409.09801

A. Eschenlohr, R. Shi, J. Chen, P. Zhou, U. Bovensiepen, W. Hübner, G. Lefkidis

{"title":"Resonant molecular transitions in second harmonic generation spectroscopy of Fe-octaethylporphyrin adsorbed on Cu(001)","authors":"A. Eschenlohr, R. Shi, J. Chen, P. Zhou, U. Bovensiepen, W. Hübner, G. Lefkidis","doi":"arxiv-2409.09801","DOIUrl":"https://doi.org/arxiv-2409.09801","url":null,"abstract":"Metal-organic molecular adsorbates on metallic surfaces offer the potential\u0000to both generate materials for future (spin-)electronics applications as well\u0000as a better fundamental understanding of molecule-substrate interaction,\u0000provided that the electronic properties of such interfaces can be analyzed\u0000and/or manipulated in a targeted manner. To investigate electronic interactions\u0000at such interfaces, we measure optical second harmonic generation (SHG) from\u0000iron-octaethylporphyrin (FeOEP) adsorbed on Cu(001), and perform electronic\u0000structure calculations using coupled cluster methods including optical\u0000excitations. We find that the SHG response of FeOEP/Cu(001) is modified at\u00002.15-2.35 eV fundamental photon energy compared to the bare Cu(001) surface.\u0000Our polarization-dependent analysis shows that the $chi_{zzz}^{(2)}$\u0000non-linear susceptibility tensor element dominates this modification. The\u0000first-principles calculations confirm this effect and conclude a resonantly\u0000enhanced SHG by molecular transitions at $hbaromega geq 2$ eV. We show that\u0000the enhancement of $chi^{(2)}_{zzz}$ results from a strong charge-transfer\u0000character of the molecule-substrate interaction. Our findings demonstrate the\u0000suitability of surface SHG for the characterization of such interfaces and the\u0000potential to employ it for time-resolved SHG experiments on optically induced\u0000electronic dynamics.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Speed of sound in gaseous cis-1,3,3,3-tetrafluoropropene (R1234ze(Z)) between 307 K and 420 K 气态顺式-1,3,3,3-四氟丙烯（R1234ze(Z)）在 307 K 和 420 K 之间的声速

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.08722

D. Lozano-Martín, D. Madonna Ripa, R. M. Gavioso

引用次数: 0

Exact analytical solution of the Chemical Master Equation for the Finke-Watkzy model 芬克-瓦特基模型化学主方程的精确解析解

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.08875

Tomasz Bednarek, Jakub Jędrak

{"title":"Exact analytical solution of the Chemical Master Equation for the Finke-Watkzy model","authors":"Tomasz Bednarek, Jakub Jędrak","doi":"arxiv-2409.08875","DOIUrl":"https://doi.org/arxiv-2409.08875","url":null,"abstract":"The Finke-Watkzy model is the reaction set consisting of autocatalysis, A + B\u0000--> 2B and the first order process A --> B. It has been widely used to describe\u0000phenomena as diverse as the formation of transition metal nanoparticles and\u0000protein misfolding and aggregation. It can also be regarded as a simple model\u0000for the spread of a non-fatal but incurable disease. The deterministic rate\u0000equations for this reaction set are easy to solve and the solution is used in\u0000the literature to fit experimental data. However, some applications of the\u0000Finke-Watkzy model may involve systems with a small number of molecules or\u0000individuals. In such cases, a stochastic description using a Chemical Master\u0000Equation or Gillespie's Stochastic Simulation Algorithm is more appropriate\u0000than a deterministic one. This is even more so because for this particular set\u0000of chemical reactions, the differences between deterministic and stochastic\u0000kinetics can be very significant. Here, we derive an analytical solution of the\u0000Chemical Master Equation for the Finke-Watkzy model. We consider both the\u0000original formulation of the model, where the reactions are assumed to be\u0000irreversible, and its generalization to the case of reversible reactions. For\u0000the former, we obtain analytical expressions for the time dependence of the\u0000probabilities of the number of A molecules. For the latter, we derive the\u0000corresponding steady-state probability distribution. Our findings may have\u0000implications for modeling the spread of epidemics and chemical reactions in\u0000living cells.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Impact of Subsurface Oxygen on CO2 Charging Energy Changes in Cu Surfaces 表层下氧气对铜表面二氧化碳充电能量变化的影响

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.08433

Xiaohe Lei, Vojtech Vlcek

{"title":"Impact of Subsurface Oxygen on CO2 Charging Energy Changes in Cu Surfaces","authors":"Xiaohe Lei, Vojtech Vlcek","doi":"arxiv-2409.08433","DOIUrl":"https://doi.org/arxiv-2409.08433","url":null,"abstract":"Subsurface oxygen in oxide-derived copper catalysts significantly influences\u0000CO$_2$ activation. However, its effect on the molecular charging process, the\u0000key to forming the CO$_2^{delta-}$ intermediate, remains poorly understood. We\u0000employ many-body perturbation theory to investigate the impact of the\u0000structural factors induced by the subsurface oxygen on charged activation of\u0000CO$_2$. By computing the molecular single-particle state energy of the\u0000electron-accepting orbital ($sigma*$) on Cu (111) surface, we examined how\u0000this molecular quasi-particle (QP) energy changes with varied vicinity of\u0000adsorption and multiple subsurface oxygen configuration. We demonstrate that\u0000subsurface oxygen impairs CO$_2$ charging, with its presence and density being\u0000influential factors. The non-local potential proves substantial for accurate\u0000excitation energy predictions yet is not sensitive to minor atomic structural\u0000changes. More importantly, state delocalization and hybridization are critical\u0000for determining QP energy. These insights are enlightening for designing atomic\u0000architectures to optimize catalytic performance on modified surfaces.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Polaritonic control of blackbody infrared radiative dissociation 黑体红外辐射解离的极性控制

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.09000

Enes Suyabatmaz, Gustavo J. R. Aroeira, Raphael F. Ribeiro

引用次数: 0

High-Temperature Non-Equilibrium Atom-Diatom Collisional Energy Transfer 高温非平衡原子-原子碰撞能量转移

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.08955

Xiaorui Zhao, Xuefei Xu, Haitao Xu

{"title":"High-Temperature Non-Equilibrium Atom-Diatom Collisional Energy Transfer","authors":"Xiaorui Zhao, Xuefei Xu, Haitao Xu","doi":"arxiv-2409.08955","DOIUrl":"https://doi.org/arxiv-2409.08955","url":null,"abstract":"The change of the vibrational energy within a molecule after collisions with\u0000another molecule plays an essential role in the evolution of molecular internal\u0000energy distributions, which is also the limiting process in the relaxation of\u0000the gas towards equilibrium. Here we investigate the energy transfer between\u0000the translational motion and the vibrational motion of the diatom during the\u0000atom-diatom collision, the simplest case involving the transfer between\u0000inter-molecular and intra-molecular energies. We are interested in the\u0000situation when the translational temperature of the gas is high, in which case\u0000there are significant probabilities for the vibrational energy to change over\u0000widely separated energy levels after a collision. Data from quasi-classical\u0000trajectory simulations of the N+N$_2$ system with textit{ab initio} potential\u0000energies suggest that the transition probability dependence on the collisional\u0000energy possesses an ``activation-saturation'' behavior and can be described by\u0000a simple model. The model allows for explicit evaluation of the vibrational\u0000state-to-state transition rate coefficients, from which the evolution of the\u0000vibrational energy distribution from any initial conditions can be solved by\u0000the master equation approach. An example of the vibrational energy relaxation\u0000in the N+N$_2$ system mimicking the gas behind strong shocks in a hypersonic\u0000flow is shown and the results are in good agreement with available data.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photo-induced molecular growth of benzonitrile in the gas phase 气相中苯腈的光诱导分子生长

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-13 DOI: arxiv-2409.08590

Nihar Ranjan Behera, Arun Kumar Kanakati, Pratikkumar Thakkar, Siddhartha Sankar Payra, Saurav Dutta, Saroj Barik, Yash Lenka, G Aravind

引用次数: 0

Unifying the description of hydrocarbons and hydrogenated carbon materials with a chemically reactive machine learning interatomic potential 用化学反应机器学习原子间势统一描述碳氢化合物和氢化碳材料

arXiv - PHYS - Chemical Physics Pub Date : 2024-09-12 DOI: arxiv-2409.08194

Rina Ibragimova, Mikhail S. Kuklin, Tigany Zarrouk, Miguel A. Caro

{"title":"Unifying the description of hydrocarbons and hydrogenated carbon materials with a chemically reactive machine learning interatomic potential","authors":"Rina Ibragimova, Mikhail S. Kuklin, Tigany Zarrouk, Miguel A. Caro","doi":"arxiv-2409.08194","DOIUrl":"https://doi.org/arxiv-2409.08194","url":null,"abstract":"We present a general-purpose machine learning (ML) interatomic potential for\u0000carbon and hydrogen which is capable of simulating various materials and\u0000molecules composed of these elements. This ML interatomic potential is trained\u0000using the Gaussian approximation potential (GAP) framework and an extensive\u0000dataset of C-H configurations obtained from density functional theory. The\u0000dataset is constructed through iterative training and structure-search\u0000techniques that generate a broad range of configurations to comprehensively\u0000sample the potential energy surface. Furthermore, the dataset is supplemented\u0000with relevant bulk, molecular, and high-pressure structures. Finally,\u0000long-range van der Waals interactions are added as a locally parametrized\u0000model. The accuracy and generality of the potential are validated through the\u0000analysis of different simulations under a wide range of conditions, including\u0000weak interactions, high temperature, and high pressure. We show that our CH GAP\u0000model describes different problems such as the formation of simple and complex\u0000alkanes, aromatic hydrocarbons, hydrogenated amorphous carbon (a-C:H), and CH\u0000systems at extreme conditions, while retaining good accuracy for pure carbon\u0000materials. We use this model to generate hydrocarbons of different sizes and\u0000complexity without prior knowledge of organic chemistry rules, and to highlight\u0000intrinsic limitations to the simultaneous description on intra and\u0000intermolecular interactions within a single computational framework. Our\u0000general-purpose ML interatomic potential has the capability to significantly\u0000advance research in the field of H-containing carbon materials and compounds,\u0000particularly in the areas where longer dynamics, reactivity and large-scale\u0000effects may be important.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0