The Journal of Physical Chemistry A最新文献_第6页

Addressing Anharmonic Effects with Density-Fitted Multicomponent Density Functional Theory 用密度拟合多分量密度泛函理论求解非调和效应

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-07 DOI: 10.1021/acs.jpca.5c0038210.1021/acs.jpca.5c00382

Lukas Hasecke*, Maximilian Breitenbach, Martí Gimferrer, Rainer Oswald and Ricardo A. Mata*,

{"title":"Addressing Anharmonic Effects with Density-Fitted Multicomponent Density Functional Theory","authors":"Lukas Hasecke*, Maximilian Breitenbach, Martí Gimferrer, Rainer Oswald and Ricardo A. Mata*, ","doi":"10.1021/acs.jpca.5c0038210.1021/acs.jpca.5c00382","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00382https://doi.org/10.1021/acs.jpca.5c00382","url":null,"abstract":"In this contribution we present the first local density-fitted multicomponent density functional theory implementation and assess its use for the calculation of anharmonic zero-point energies. Four challenging cases of molecular aggregates are reviewed: deprotonated formic acid trimer, diphenyl ether-tert-butyl alcohol conformers, anisole/methanol and anisole/2-naphtol dimers. These are all cases where a mismatch between the low-temperature computationally predicted minimum and the experimentally determined structure was observed. Through the use of nuclear-electronic orbital energies in the thermodynamic correction, the correct energetic ordering is recovered. For the smallest system, we compare our results to vibrational perturbation theory anharmonically corrected zero-point energy, with perfect agreement for the lower-lying conformers. The performance of the newly developed code and the density fitting errors are also analyzed. Overall, the new implementation shows a very good scaling with system size and the density fitting approximations exhibit a negligible impact.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 15","pages":"3560–3566 3560–3566"},"PeriodicalIF":2.7,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.5c00382","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Energetic and Electronic Properties of UX+/0/– for X = Li and Be and Comparison of the Properties of the Uranium Atom Binding to 2nd Row Elements Li–F X = Li和Be的UX+/0/ -的能量和电子性质及铀原子与第二行元素Li - f结合的性质比较

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-06 DOI: 10.1021/acs.jpca.4c0836410.1021/acs.jpca.4c08364

João G. F. Romeu, Gabriel F. de Melo, Kirk A. Peterson and David A. Dixon*,

{"title":"Energetic and Electronic Properties of UX+/0/– for X = Li and Be and Comparison of the Properties of the Uranium Atom Binding to 2nd Row Elements Li–F","authors":"João G. F. Romeu, Gabriel F. de Melo, Kirk A. Peterson and David A. Dixon*, ","doi":"10.1021/acs.jpca.4c0836410.1021/acs.jpca.4c08364","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08364https://doi.org/10.1021/acs.jpca.4c08364","url":null,"abstract":"The bonding and spectroscopic properties of ULi+/0/– and UBe+/0/– to complete the series for UX+/0/– for X = Li to F were investigated by high-level ab initio SO-CASPT2 and CCSD(T) electronic structure calculations. The low-lying spin–orbit states were obtained at the SA-CASPT2/aQ-PP level; bond dissociation energies (BDEs), ionization energies (IEs), adiabatic electronic affinities (AEAs), and vertical detachment energies (VDEs) were calculated at the Feller-Peterson-Dixon (FPD) level. A dense manifold of low-lying states was predicted for ULi+/0/– and UBe+/0/–. The calculated BDEs for ULi (37.7 kJ/mol) and UBe (8.0 kJ/mol) show that UBe is weakly bound. For redox processes, the BDEs increased for ULi+ (109.3 kJ/mol), ULi– (47.4 kJ/mol), UBe+ (35.6 kJ/mol), and UBe– (72.3 kJ/mol). The IE(ULi) = 4.650 eV is lower than IE(Li); the IE(UBe) = 5.901 eV is close to the IE(U) and to the IEs of UB, UC, UN, UO, and UF. The AEAs of ULi (0.708 eV) and UBe (0.989 eV) are lower than those for UB, UC, UN, and UO but higher than that for EA(UF). Natural bond orbital (NBO) calculations show that ULi has the 5f36d17s2 configuration for U and 2s1 for Li, with a small partial negative charge slightly delocalized on U. UBe arises from the U(5f36d17s2) and Be(2s2) electron configurations with no charge separation. The same calculations were made for WX (X = Li, Be, C–F) to enable detailed comparisons of the properties for UX with WX (X = Li–F). For WX, BDE(WX) is higher than that for UX for X = Li to N and lower than BDE(UX) for X = O and F, mostly due to the higher IE of W than U as ionic character becomes more important going from Li to F.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 17","pages":"3763–3779 3763–3779"},"PeriodicalIF":2.7,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Time-dependent Bivariational Principle: Theoretical Foundation for Real-Time Propagation Methods of Coupled-Cluster Type. 时变二分原理：耦合簇型实时传播方法的理论基础。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-06 DOI: 10.1021/acs.jpca.4c07417

Simen Kvaal, Håkon Richard Fredheim, Mads Greisen Højlund, Thomas Bondo Pedersen

{"title":"Time-dependent Bivariational Principle: Theoretical Foundation for Real-Time Propagation Methods of Coupled-Cluster Type.","authors":"Simen Kvaal, Håkon Richard Fredheim, Mads Greisen Højlund, Thomas Bondo Pedersen","doi":"10.1021/acs.jpca.4c07417","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07417","url":null,"abstract":"Real-time propagation methods for chemistry and physics are invariably formulated using variational techniques. The time-dependent bivariational principle (TD-BIVP) is known to be the proper framework for coupled-cluster type methods, and is here studied from a differential geometric point of view. It is demonstrated how two distinct classical Hamilton's equations of motion arise from considering the real and imaginary parts of the action integral. This in turn leads to two distinct bivariational principles for real bivariational approximation submanifolds. Conservation laws and Poisson brackets are introduced, completing the analogy with classical mechanics. Furthermore, the time-dependent univariational principles (the time-dependent variational principle, the McLachlan principle, and the Dirac-Frenkel principle) are reconstructed using the TD-BIVP and a bivariational submanifold on product form. An overview of established real-time propagation methods is given in the context of our formulation of the TD-BIVP, namely time-dependent traditional coupled-cluster theory, orbital-adaptive coupled-cluster theory, time-dependent orthogonal optimized coupled-cluster theory, Brueckner coupled-cluster theory, and equation-of-motion coupled cluster theory.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Time-dependent Bivariational Principle: Theoretical Foundation for Real-Time Propagation Methods of Coupled-Cluster Type 时变二分原理：耦合簇型实时传播方法的理论基础

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-06 DOI: 10.1021/acs.jpca.4c0741710.1021/acs.jpca.4c07417

Simen Kvaal*, Håkon Richard Fredheim, Mads Greisen Højlund and Thomas Bondo Pedersen,

{"title":"Time-dependent Bivariational Principle: Theoretical Foundation for Real-Time Propagation Methods of Coupled-Cluster Type","authors":"Simen Kvaal*, Håkon Richard Fredheim, Mads Greisen Højlund and Thomas Bondo Pedersen, ","doi":"10.1021/acs.jpca.4c0741710.1021/acs.jpca.4c07417","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07417https://doi.org/10.1021/acs.jpca.4c07417","url":null,"abstract":"Real-time propagation methods for chemistry and physics are invariably formulated using variational techniques. The time-dependent bivariational principle (TD-BIVP) is known to be the proper framework for coupled-cluster type methods, and is here studied from a differential geometric point of view. It is demonstrated how two distinct classical Hamilton’s equations of motion arise from considering the real and imaginary parts of the action integral. This in turn leads to two distinct bivariational principles for real bivariational approximation submanifolds. Conservation laws and Poisson brackets are introduced, completing the analogy with classical mechanics. Furthermore, the time-dependent univariational principles (the time-dependent variational principle, the McLachlan principle, and the Dirac–Frenkel principle) are reconstructed using the TD-BIVP and a bivariational submanifold on product form. An overview of established real-time propagation methods is given in the context of our formulation of the TD-BIVP, namely time-dependent traditional coupled-cluster theory, orbital-adaptive coupled-cluster theory, time-dependent orthogonal optimized coupled-cluster theory, Brueckner coupled-cluster theory, and equation-of-motion coupled cluster theory.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 15","pages":"3508–3521 3508–3521"},"PeriodicalIF":2.7,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07417","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Energetic and Electronic Properties of UX^+/0/- for X = Li and Be and Comparison of the Properties of the Uranium Atom Binding to 2nd Row Elements Li-F. X = Li和Be的UX+/0/-的能量和电子性质及铀原子与第二行元素Li- f结合的性质比较

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-06 DOI: 10.1021/acs.jpca.4c08364

João G F Romeu, Gabriel F de Melo, Kirk A Peterson, David A Dixon

{"title":"Energetic and Electronic Properties of UX+/0/- for X = Li and Be and Comparison of the Properties of the Uranium Atom Binding to 2nd Row Elements Li-F.","authors":"João G F Romeu, Gabriel F de Melo, Kirk A Peterson, David A Dixon","doi":"10.1021/acs.jpca.4c08364","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08364","url":null,"abstract":"The bonding and spectroscopic properties of ULi+/0/- and UBe+/0/- to complete the series for UX+/0/- for X = Li to F were investigated by high-level ab initio SO-CASPT2 and CCSD(T) electronic structure calculations. The low-lying spin-orbit states were obtained at the SA-CASPT2/aQ-PP level; bond dissociation energies (BDEs), ionization energies (IEs), adiabatic electronic affinities (AEAs), and vertical detachment energies (VDEs) were calculated at the Feller-Peterson-Dixon (FPD) level. A dense manifold of low-lying states was predicted for ULi+/0/- and UBe+/0/-. The calculated BDEs for ULi (37.7 kJ/mol) and UBe (8.0 kJ/mol) show that UBe is weakly bound. For redox processes, the BDEs increased for ULi+ (109.3 kJ/mol), ULi- (47.4 kJ/mol), UBe+ (35.6 kJ/mol), and UBe- (72.3 kJ/mol). The IE(ULi) = 4.650 eV is lower than IE(Li); the IE(UBe) = 5.901 eV is close to the IE(U) and to the IEs of UB, UC, UN, UO, and UF. The AEAs of ULi (0.708 eV) and UBe (0.989 eV) are lower than those for UB, UC, UN, and UO but higher than that for EA(UF). Natural bond orbital (NBO) calculations show that ULi has the 5f36d17s2 configuration for U and 2s1 for Li, with a small partial negative charge slightly delocalized on U. UBe arises from the U(5f36d17s2) and Be(2s2) electron configurations with no charge separation. The same calculations were made for WX (X = Li, Be, C-F) to enable detailed comparisons of the properties for UX with WX (X = Li-F). For WX, BDE(WX) is higher than that for UX for X = Li to N and lower than BDE(UX) for X = O and F, mostly due to the higher IE of W than U as ionic character becomes more important going from Li to F.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-Frequency Tails in Spectral Densities. 频谱密度中的高频尾。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-04 DOI: 10.1021/acs.jpca.5c00943

Roman Korol, Xinxian Chen, Ignacio Franco

{"title":"High-Frequency Tails in Spectral Densities.","authors":"Roman Korol, Xinxian Chen, Ignacio Franco","doi":"10.1021/acs.jpca.5c00943","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00943","url":null,"abstract":"Recent advances in numerically exact quantum dynamics methods have brought the dream of accurately modeling the dynamics of chemically complex open systems within reach. Path-integral-based methods, hierarchical equations of motion, and quantum analog simulators all require the spectral density (SD) of the environment to describe its effect on the system. Here, we focus on the decoherence dynamics of electronically excited species in solution in the common case where nonradiative electronic relaxation dominates and is much slower than electronic dephasing. We show that the computed relaxation rate is highly sensitive to the choice of SD representation─such as the Drude-Lorentz or Brownian modes─or strategy used to capture the main SD features, even when early-time dephasing dynamics remains robust. The key reason is that electronic relaxation is dominated by the resonant contribution from the high-frequency tails of the SD, which are orders of magnitude weaker than the main features of the SD and can vary significantly between strategies. This finding highlights an important, yet overlooked, numerical challenge: obtaining an accurate SD requires capturing its structure over several orders of magnitude to ensure correct decoherence dynamics at both early and late times. To address this, we provide a simple transformation that recovers the correct relaxation rates in quantum simulations constrained by algorithmic or physical limitations on the shape of the SD. Our findings enable a comparison of different numerically exact simulation methods and expand the capabilities of analog simulations of open quantum dynamics.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143784382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF₃. NF3电离能测定的理论与实验差异。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-04 DOI: 10.1021/acs.jpca.5c00613

Megan R Bentley, Peter R Franke, Kaila E Weflen, David H Bross, Branko Ruscic, John F Stanton

{"title":"Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF3.","authors":"Megan R Bentley, Peter R Franke, Kaila E Weflen, David H Bross, Branko Ruscic, John F Stanton","doi":"10.1021/acs.jpca.5c00613","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00613","url":null,"abstract":"High-accuracy ab initio thermochemical predictions for the ionization energy of NF3, the barrier height (to inversion) of NF3+, and the dissociative ionization threshold of NF3 to NF2+ + F are presented and incorporated into Active Thermochemical Tables. The adiabatic ionization energy of the first ionization band of NF3, calculated at 12.647 ± 0.010 eV, is at odds with previous experimental interpretations by nearly 0.36 eV due to unfavorable Franck-Condon factors associated with this transition. The barrier (to inversion) height is calculated to be about 0.6 eV lower in energy than the prior interpretation, which instigates a discussion of the supposed vibrational structure of the first ionization band of NF3. Updated assignments of the photoelectron spectrum are proposed, and the loss in vibrational spacing on the high-energy side of the experimental ionization band is discussed. Rudimentary anharmonic Franck-Condon simulations qualitatively reproduce the broad spectral features observed in experiment.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143784379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-Frequency Tails in Spectral Densities 频谱密度中的高频尾

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-04 DOI: 10.1021/acs.jpca.5c0094310.1021/acs.jpca.5c00943

Roman Korol*, Xinxian Chen and Ignacio Franco*,

{"title":"High-Frequency Tails in Spectral Densities","authors":"Roman Korol*, Xinxian Chen and Ignacio Franco*, ","doi":"10.1021/acs.jpca.5c0094310.1021/acs.jpca.5c00943","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00943https://doi.org/10.1021/acs.jpca.5c00943","url":null,"abstract":"Recent advances in numerically exact quantum dynamics methods have brought the dream of accurately modeling the dynamics of chemically complex open systems within reach. Path-integral-based methods, hierarchical equations of motion, and quantum analog simulators all require the spectral density (SD) of the environment to describe its effect on the system. Here, we focus on the decoherence dynamics of electronically excited species in solution in the common case where nonradiative electronic relaxation dominates and is much slower than electronic dephasing. We show that the computed relaxation rate is highly sensitive to the choice of SD representation─such as the Drude–Lorentz or Brownian modes─or strategy used to capture the main SD features, even when early–time dephasing dynamics remains robust. The key reason is that electronic relaxation is dominated by the resonant contribution from the high-frequency tails of the SD, which are orders of magnitude weaker than the main features of the SD and can vary significantly between strategies. This finding highlights an important, yet overlooked, numerical challenge: obtaining an accurate SD requires capturing its structure over several orders of magnitude to ensure correct decoherence dynamics at both early and late times. To address this, we provide a simple transformation that recovers the correct relaxation rates in quantum simulations constrained by algorithmic or physical limitations on the shape of the SD. Our findings enable a comparison of different numerically exact simulation methods and expand the capabilities of analog simulations of open quantum dynamics.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 15","pages":"3587–3596 3587–3596"},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.5c00943","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF3 NF3电离能测定的理论与实验差异

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-04 DOI: 10.1021/acs.jpca.5c0061310.1021/acs.jpca.5c00613

Megan R. Bentley*, Peter R. Franke, Kaila E. Weflen, David H. Bross, Branko Ruscic* and John F. Stanton,

{"title":"Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF3","authors":"Megan R. Bentley*, Peter R. Franke, Kaila E. Weflen, David H. Bross, Branko Ruscic* and John F. Stanton, ","doi":"10.1021/acs.jpca.5c0061310.1021/acs.jpca.5c00613","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00613https://doi.org/10.1021/acs.jpca.5c00613","url":null,"abstract":"High-accuracy ab initio thermochemical predictions for the ionization energy of NF3, the barrier height (to inversion) of NF3+, and the dissociative ionization threshold of NF3 to NF2+ + F are presented and incorporated into Active Thermochemical Tables. The adiabatic ionization energy of the first ionization band of NF3, calculated at 12.647 ± 0.010 eV, is at odds with previous experimental interpretations by nearly 0.36 eV due to unfavorable Franck–Condon factors associated with this transition. The barrier (to inversion) height is calculated to be about 0.6 eV lower in energy than the prior interpretation, which instigates a discussion of the supposed vibrational structure of the first ionization band of NF3. Updated assignments of the photoelectron spectrum are proposed, and the loss in vibrational spacing on the high-energy side of the experimental ionization band is discussed. Rudimentary anharmonic Franck–Condon simulations qualitatively reproduce the broad spectral features observed in experiment.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 15","pages":"3474–3484 3474–3484"},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Response of a Tethered Zn-Bis-Terpyridine Complex to an External Mechanical Force: A Computational Study of the Roles of the Tether and Solvent 系链锌-双三吡啶配合物对机械外力的响应：系链和溶剂作用的计算研究

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-04-04 DOI: 10.1021/acs.jpca.4c0863910.1021/acs.jpca.4c08639

Shouryo Ghose, Anne-Sophie Duwez, Charles-André Fustin and Françoise Remacle*,

{"title":"Response of a Tethered Zn-Bis-Terpyridine Complex to an External Mechanical Force: A Computational Study of the Roles of the Tether and Solvent","authors":"Shouryo Ghose, Anne-Sophie Duwez, Charles-André Fustin and Françoise Remacle*, ","doi":"10.1021/acs.jpca.4c0863910.1021/acs.jpca.4c08639","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08639https://doi.org/10.1021/acs.jpca.4c08639","url":null,"abstract":"Polymeric materials containing weak sacrificial bonds can be designed to engineer self-healing and higher toughness, improve melt-processing, or facilitate recycling. However, they usually exhibit a lower mechanical strength and are subject to creep and fatigue. For improving their design, it is of interest to investigate their mechanical response on the molecular scale. We report on a computational study of the response to a mechanical external force of a Zinc(II) bis-methyl phenyl-terpyridine ([Zn-bis-Terpy]2+) complex included in a cyclic poly(ethylene glycol) (PEG) tether designed to maintain the two partners of the metal–ligand bonds in close proximity after the rupture of the complex. The mechanical response is studied as a function of the pulling distortion by using the CoGEF isometric protocol, including interactions with a polar solvent (DMSO). We show that tethering favors recombination but destabilizes the complex before bond rupture because of the interactions of the PEG units with Terpy ligands. Similar effects occur between the DMSO molecules and the complex. Our results on the molecular scale are relevant for single-molecule force spectroscopy experiments. Interactions of the complex with solvent molecules and/or with the tether lead to a dispersion of the rupture force values, which could obscure the interpretation of the results.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 15","pages":"3423–3434 3423–3434"},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0