The Journal of Physical Chemistry A最新文献

{"title":"Detection of a Planar Tetracoordinate Hydrogen within the Indium Framework by Quantum Dynamics Theory.","authors":"Xingyu Zhang, Zekai Miao, Qingyong Meng","doi":"10.1021/acs.jpca.4c06742","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c06742","url":null,"abstract":"<p><p>In this work, we consider the question how to detect the planar tetracoordination hydrogen geometry which was recently proposed by electronic structure calculations on the In₄H⁺ system (<i>Angew. Chem. Int. Ed.</i> <b>2024</b>, <i>63</i>, e202317312; e202400927; e202403214). Keeping the <i>C</i>_4v symmetry, a two-dimensional model of In₄H⁺ is designed to build the nonadiabatic Hamiltonian operator with the lowest-lying singlet and triplet states coupled with spin-orbit coupling. The electronic energies in fitting the potential energy matrix are computed at either the MRCI or CCSD (T) level. Having constructed Hamiltonian, the multiconfigurational time-dependent Hartree product method predicts vibrational eigenstates for spectrum and recrossing probability of the proton. These quantum dynamics calculations predict a period of ∼60 fs for the proton recrossing the In₄ moiety and further indicate that experimental observation of the <i>D</i>_4h geometry for the triplet state is highly probable at room temperature even though the present MRCI and previous CASPT2 calculations (<i>Angew. Chem. Int. Ed.</i> <b>2024</b>, <i>63</i>, e202400927) both predict the <i>C</i>_4v symmetry. To measure the <i>C</i>_4v geometry, a low temperature of ≲30 K could be adopted. Despite the low temperature, the experiment might still miss the <i>C</i>_4v geometry due to the nonzero recrossing probability of H at the low kinetic energy region. Further, a new type of hydrogen bonding in the <i>D</i>_4h geometry is proposed to explain the interaction between the <i>C</i>_4v geometries.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602092","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}

{"title":"Mechanism for Site-Selective Hydroboration of C₇₀ Fullerene with Borane by DFT-D3 Study.","authors":"Jong Woan Choi, Bo Mi Kim, Eiji Osawa, Ji Young Lee, Changhoon Lee, Kee Hag Lee","doi":"10.1021/acs.jpca.4c04351","DOIUrl":"10.1021/acs.jpca.4c04351","url":null,"abstract":"&lt;p&gt;&lt;p&gt;We studied the hydroboration of the C&lt;sub&gt;70&lt;/sub&gt; fullerene using both B3LYP-D3(BJ)/6-311G(d,p) and M06-2X-D3/6-311G(d,p) levels of theory, incorporating the empirical dispersion interaction, and Fukui index calculations. Potential energy surfaces (PESs) and Gibbs free energy surfaces (GFESs) were calculated for the pathways from four BH&lt;sub&gt;3&lt;/sub&gt; adducts (located at the &lt;b&gt;&lt;i&gt;AB&lt;/i&gt;&lt;/b&gt;, &lt;b&gt;&lt;i&gt;CC&lt;/i&gt;&lt;/b&gt;, &lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;, and &lt;b&gt;&lt;i&gt;E&lt;/i&gt;&lt;/b&gt; sites) on the C&lt;sub&gt;70&lt;/sub&gt; to eight products formed by the 1,2-addition of BH&lt;sub&gt;3&lt;/sub&gt; across the four [6,6]-ring fused bonds (&lt;b&gt;&lt;i&gt;AB&lt;/i&gt;&lt;/b&gt;, &lt;b&gt;&lt;i&gt;CC&lt;/i&gt;&lt;/b&gt;, &lt;b&gt;&lt;i&gt;DE&lt;/i&gt;&lt;/b&gt;, and &lt;b&gt;&lt;i&gt;EE&lt;/i&gt;&lt;/b&gt;) and across the two [5,6]-ring fused bonds (&lt;b&gt;&lt;i&gt;AA&lt;/i&gt;&lt;/b&gt; and &lt;b&gt;&lt;i&gt;DD&lt;/i&gt;&lt;/b&gt;). These pathways are two-step consecutive reactions. We denoted the positions on the fullerene cage as &lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt; through &lt;i&gt;E&lt;/i&gt;, from the pole to the equator, based on the D&lt;sub&gt;5h&lt;/sub&gt; symmetry of the C&lt;sub&gt;70&lt;/sub&gt; fullerene. In the first step reaction, the product ratios for the four adduct intermediates should be as the primary intermediate BH&lt;sub&gt;3&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;), the secondary intermediate BH&lt;sub&gt;3&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;AB&lt;/i&gt;&lt;/b&gt;), the tertiary intermediate BH&lt;sub&gt;3&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;CC&lt;/i&gt;&lt;/b&gt;), and the minor intermediate BH&lt;sub&gt;3&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;E&lt;/i&gt;&lt;/b&gt;), based on the Fukui indices. In addition, in the second step reaction, transition states (TSs) from four adduct intermediates to eight product isomers, namely, BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;) to BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;E&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;E&lt;/i&gt;&lt;/b&gt;), were obtained using the QST2 method. The calculated reaction coordinates showed exothermic reactions for all bonds except the &lt;b&gt;&lt;i&gt;EE&lt;/i&gt;&lt;/b&gt; bond. We also confirmed the transition states by frequency calculations and intrinsic reaction coordinate (IRC) analyses. The PESs and GFESs suggest spontaneous processes for the four isomers, of which the primary products are BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;) and its isomer BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt;), the secondary product is BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;C&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;C&lt;/i&gt;&lt;/b&gt;), and the tertiary product is BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;), all formed through adduct intermediates. Therefore, through the hydroboration reaction of C&lt;sub&gt;70&lt;/sub&gt;, we could predict and design the site selectivity of C&lt;sub&gt;70&lt;/sub&gt; by controlling the energy barrier of the transition state in the second step of the reaction. This implies that we could selectively synthesize mainly BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;)H (&lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt;) isomers across the AB-[6,6]-ring fused bond and also design BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;)H(&lt;b&gt;&lt;i&gt;D&lt;/i&gt;&lt;/b&gt;) isomers across the DD-[5,6]-ring fused bond. Also, the calculations of formation rate constants can well simulate the experimental ratio of two C&lt;sub&gt;70&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt; isomers by the hydrolysis of BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;A&lt;/i&gt;&lt;/b&gt;)H(&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;), BH&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;&lt;i&gt;B&lt;/i&gt;&lt;/b&gt;)H(&lt;b&gt;&lt;i","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491182","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}

{"title":"Mono- and Bichromophores Formed from Perylene Monoimide Diesters: Competition between Intramolecular Charge Transfer and Intermolecular Singlet Exciton Fission.","authors":"Demet Demirci Gültekin, Serkan Şen, Ayhan Elmalı, Ahmet Karatay, Muhammet Erkan Köse, Anthony Harriman, Özgür Altan Bozdemir","doi":"10.1021/acs.jpca.4c05424","DOIUrl":"10.1021/acs.jpca.4c05424","url":null,"abstract":"<p><p>Perylene monoimide diesters and the corresponding phenyl-linked bichromophores are strongly fluorescent in dilute solution with minimal triplet population after relaxation of the initial Franck-Condon state. The monomer forms nonemissive face-to-face dimers in solution, wherein illumination leads to formation of a spin-correlated, triplet pair with a yield of <i>ca</i>. 13% and with a time constant of 4 ± 1 ps. The triplet pair, which is localized on the aggregate, cannot separate and decays with a mean lifetime of 80 ± 10 ps. The relaxed S₁ state of the weakly coupled, phenyl-linked bichromophores establishes an equilibrium with an intramolecular charge-transfer state over a hundred picoseconds or so, depending on the solvent and the geometry of the linkage. This equilibrium mixture, being dominated by the relaxed S₁ state, decays on the nanosecond time scale in solution at room temperature without implication of a triplet state. Self-association occurs at higher concentration and, for the <i>para</i>-bridged bichromophore, leads to inefficient triplet formation in tetrahydrofuran at room temperature.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11551949/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491184","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}

{"title":"Multireference Fock Space Coupled-Cluster Method for the (3,0) Sector.","authors":"Monika Musial, Stanisław A Kucharski","doi":"10.1021/acs.jpca.4c04357","DOIUrl":"10.1021/acs.jpca.4c04357","url":null,"abstract":"<p><p>This work reports an implementation of a novel realization of the multireference coupled cluster theory formulated in Fock space. Extending the previous formulation carried out in the (1,1) [M. Musial, R. J. Bartlett, J. Chem. Phys. <b>129</b>, 044101 (2008)], (0,2) [M. Musial, R. J. Bartlett, J. Chem. Phys. <b>135</b>, 044121 (2011)], and (2,0) [M. Musial, J. Chem. Phys. <b>136</b>, 134111 (2012)] sectors to the (3,0) sector, we are able to treat structures with three valence electrons. The (3,0) sector describes systems with three electrons added to the reference, which means that in order to perform correlated calculations for the neutral <i>AB</i> molecule, we have to adopt as the reference a triply ionized structure <i>AB</i>³⁺. A desirable situation occurs when such an ion has a closed-shell structure and also dissociates into closed shell fragments. This feature makes it possible to apply the restricted Hartree-Fock scheme for the whole range of interatomic distances. Examples of molecules of this type are the diatomics formed by the atoms of alkali metals and alkaline earth metals. An analogous structure is also exhibited by alkali metal monocarbides. In the current work, we have calculated the potential energy curves and spectroscopic constants for the LiBe, LiC, and NaC molecules.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11551963/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491185","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}

{"title":"Electric Field Influence on CO Clathrate Hydrates.","authors":"Smita Rai, Dhurba Rai","doi":"10.1021/acs.jpca.4c05074","DOIUrl":"10.1021/acs.jpca.4c05074","url":null,"abstract":"<p><p>We consider carbon monoxide (CO) confined in the hydrogen-bonded building blocks of sI and sII clathrate hydrates, viz., (5¹², 5¹²6², 5¹²6⁴) cages, within the density functional theory-based calculations. We study their response to the applied electric fields in terms of changes in the geometrical parameters, dipole moment, HOMO-LUMO gap, and vibrational frequency shift. We examine the stability of CO clathrate hydrate building block cages and identify a possible indication of the field-induced release of CO.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491178","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}

{"title":"Mixed H₂S and H₂O Clusters─New Insights into Dispersion-Dominated Hydrogen Bonding.","authors":"Philipp Meyer, Svenja Jäger, Jai Khatri, Stefan Henkel, Gerhard Schwaab, Martina Havenith","doi":"10.1021/acs.jpca.4c05510","DOIUrl":"10.1021/acs.jpca.4c05510","url":null,"abstract":"<p><p>Here, we report the results of an IR spectroscopy study on heteroclusters of H₂S and H₂O and several of their isotopomers using mass-selective IR spectroscopy in superfluid helium nanodroplets in the range of 2560-2800 cm^-1. Based on DFT calculations on the B3LYP-D3/6-311++G(d,p) level of theory, we were able to assign the experimentally observed O-D stretching bands to heterodimer and heterotrimer clusters. Since no bands of the S-H-bound conformer HSH···OH₂ could be observed, we were able to determine the O-H-bound conformer HOH···SH₂ to be the global minimum structure. A trapping of the local minima in helium nanodroplets was not observed. This is in line with the weaker hydrogen bond expected for H₂S complexes. In these clusters, the interaction energy is expected to be more dominated by dispersion and less dictated by highly directional electrostatic forces.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491183","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}

{"title":"Rate Constants of the H + HCF₃ → H₂ + CF₃ Reaction from Ring Polymer Molecular Dynamics on a Highly Accurate Potential Energy Surface.","authors":"Yongfa Zhu, Hongwei Song","doi":"10.1021/acs.jpca.4c05352","DOIUrl":"10.1021/acs.jpca.4c05352","url":null,"abstract":"<p><p>The reaction between H and HCF₃ is the primary consumption pathway of HCF₃ in the atmosphere and combustion. In this work, ring polymer molecular dynamics (RPMD) calculations are performed to calculate the rate constants of the reaction on a recently developed accurate potential energy surface. 36, 20, and 8 beads are used to compute the rate constants at 350 K ≤ <i>T</i> < 800 K, 800 K ≤ <i>T</i> ≤ 1000 K, and <i>T</i> > 1000 K, respectively. The obtained RPMD rate constants agree well with the experimental measurements. In addition, a detailed analysis of the free-energy curves and transmission coefficients reveals that the quantum tunneling significantly affects the reaction dynamics, even at high temperatures.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520268","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}

{"title":"Balancing Brightness and Photobasicity: Modulating Excited-State Proton Transfer Pathways in Push-Pull Fluorophores for Biological Two-Photon Imaging.","authors":"Adam M McCallum, Jiyao Yu, S Sumalekshmy, Abigail Hagwood, Christoph J Fahrni","doi":"10.1021/acs.jpca.4c05649","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c05649","url":null,"abstract":"<p><p>Push-pull fluorophores with donor-π-acceptor architectures are attractive scaffolds for the design of probes and labels for two-photon microscopy. Such fluorophores undergo a significant charge-delocalization in the excited state, which is essential for achieving a large two-photon absorption cross-section and brightness. The polarized excited state may, however, also facilitate excited-state proton transfer (ESPT) pathways that can interfere with the probe response. Herein, we employed steady-state and time-resolved spectroscopic studies to elucidate whether ESPT is responsible for the pH-dependent emission response of the Zn(II)-selective fluorescent probe chromis-1. Composed of a push-pull architecture with a pyridine ring as the acceptor, the chromis-1 fluorophore core acts as a photobase that promotes ESPT upon acidification. Although the p<i>K</i>_a of the pyridine acceptor increases more than six orders of magnitude upon excitation, the photobasicity is not sufficient to deprotonate solvent water molecules under neutral conditions. Rather, the pH-dependent emission response is caused by the pendant bis-isonicotinic acid chelating group which upon protonation facilitates an excited-state intramolecular proton transfer to the pyridine acceptor. A simple permutation of the core pyridine nitrogen from the para- to the ortho-position relative to the thiazole substituent was sufficient to reduce the excited-state basicity by two orders of magnitude without compromising the two-photon excited brightness. These results highlight the importance of choosing the appropriate fluorophore core and chelating moiety for minimizing pH-dependent responses in the design of fluorescent probes for biological imaging.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602084","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}

{"title":"Diagrams in Polaritonic Coupled Cluster Theory.","authors":"Laurenz Monzel, Stella Stopkowicz","doi":"10.1021/acs.jpca.4c04389","DOIUrl":"10.1021/acs.jpca.4c04389","url":null,"abstract":"<p><p>We present a diagrammatic notation to derive the quantum-electrodynamic coupled cluster (QED-CC) equations needed for the description for polaritonic ground and excited states. Our presented notation is a generalization of the existing diagrammatic notation of standard electronic coupled-cluster theory. It is used to derive the QED-CC and QED-EOM-CC equations for the QED-CCSD-1-SD and QED-CCSD-12-SD truncation schemes. Furthermore, we present the diagrams for the CC Λ-equations and reduced density matrices which are needed for the calculation of molecular properties.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491176","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}

{"title":"Effect of Fluorine Substitution on Magnetizabilities: Insights from Density Functional Theory and Benchmark Coupled-Cluster Calculations.","authors":"Terri E Field-Theodore, Peter R Taylor, David J D Wilson","doi":"10.1021/acs.jpca.4c05849","DOIUrl":"10.1021/acs.jpca.4c05849","url":null,"abstract":"<p><p>The quantitative calculation of the magnetizability tensor of fluorine-containing molecules has been a longstanding challenge for quantum chemistry. We report a benchmark study on the effect of fluorine substitution on the magnetizability (both isotropic and anisotropic) of 24 small closed-shell molecules using coupled-cluster (CCSD(T)) theory, large basis sets, and London atomic orbitals. By extrapolation to a complete basis set (CBS) result, we establish the CCSD(T)/CBS limit and take the opportunity to assess the performance of various density functional theory approximations. Correcting for zero-point vibration further allows us to directly compare theory with (gas-phase) experimental data. We revisit Flygare's hypothesis on molecular magnetizabilities, which relates the successive replacement of hydrogen by fluorine atoms to changes in the magnetizability anisotropy. Some exceptions to this hypothesis are documented, and we rationalize these observations on the basis of hybridization on carbon.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491177","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}