*Phys Chem Chem Phys ; 2020 Feb 26.*

**| MEDLINE**| ID: mdl-32101195

##### RESUMO

The T1 excited state relaxation in thiophosgene has attracted much attention as a relatively simple model for the intersystem crossing (ISC) transitions in polyatomic molecules. The very short (20-40 ps) T1 lifetime predicted in several theoretical studies strongly disagrees with the experimental values (â¼20 ns) indicating that the kinetics of T1 â S0 ISC is not well understood. We use the nonadiabatic transition state theory (NA-TST) with the Zhu-Nakamura transition probability and the multireference perturbation theory (CASPT2) to show that the T1 â S0 ISC occurs in the quantum tunneling regime. We also introduce a new zero-point vibrational energy correction scheme that improves the accuracy of the predicted ISC rate constants at low internal energies. The predicted lifetimes of the T1 vibrational states are between one and two orders of magnitude larger than the experimental values. This overestimation is attributed to the multidimensional nature of quantum tunneling that facilitates ISC transitions along the non-minimum energy path and is not accounted for in the one-dimensional NA-TST.

*J Phys Chem Lett ; 10(24): 7678-7683, 2019 Dec 19.*

**| MEDLINE**| ID: mdl-31755716

##### RESUMO

Molecular nanomagnets hold great promise for spintronics and quantum technologies, provided that their spin memory can be preserved above liquid-nitrogen temperatures. In the past few years, the magnetic hysteresis records observed for two related dysprosocenium-type complexes have highlighted the potential of molecular engineering to decouple vibrational excitations from spin states and thereby enhance magnetic memory. Herein, we study the spin-vibrational coupling in [(CpiPr5)Dy(Cp*)]+ (CpiPr5 = pentaisopropylcyclopentadienyl, Cp* = pentamethylcyclopentadienyl), which currently holds the hysteresis record (80 K), by means of a computationally affordable methodology that combines first-principles electronic structure calculations with a phenomenological ligand field model. Our analysis is in good agreement with the previously reported state-of-the-art ab initio calculations, with the advantage of drastically reducing the computation time. We then apply the proposed methodology to three alternative dysprosocenium-type complexes, extracting physical insights that demonstrate the usefulness of this strategy to efficiently engineer and screen magnetic molecules with the potential of retaining spin information at higher temperatures.

*J Chem Theory Comput ; 15(11): 6074-6084, 2019 Nov 12.*

**| MEDLINE**| ID: mdl-31518121

##### RESUMO

Spin-dependent processes involving nonadiabatic transitions between electronic states with different spin multiplicities play important roles in the chemistry of complex systems. The rates of these processes can be predicted based on the molecular properties at the minimum energy crossing point (MECP) between electronic states. We present the development of the MECP search technique within the fragment molecular orbital (FMO) method applicable to large complex systems. The accuracy and scalability of the new method is demonstrated on several models of the metal-sulfur protein rubredoxin. The effect of the model size on the MECP geometry and relative energy is discussed. The fragment energy decomposition and spin density delocalization analyses reveal how different protein residues and solvent molecules contribute to stabilization of the spin states. The developed FMO-MECP method can help to clarify the role of nonadiabatic spin-dependent processes in complex systems and can be used for designing mutations aimed at controlling these processes in metalloproteins, including spin-dependent catalysis and electron transfer.

##### Assuntos

Modelos Moleculares , Teoria Quântica , Domínio Catalítico , Transporte de Elétrons , Rubredoxinas/química , Rubredoxinas/metabolismo , Termodinâmica*J Phys Chem Lett ; 10(1): 115-120, 2019 Jan 03.*

**| MEDLINE**| ID: mdl-30560674

##### RESUMO

Diffuse interstellar bands (DIBs) are puzzling absorption features believed to contain critical information about molecular evolution in space. Despite the fact that C60+ recently became the first confirmed carrier of several DIBs, the nature of the corresponding transitions is not understood. Using electronic structure methods, we show that the two strong C60+ DIBs cannot be explained by electronic transitions to the two different excited 2 E1 g states or the two spin-orbit components of the lowest 2 E1 g state, as suggested before. We argue that the strong DIBs at 9632 and 9577 Å correspond to the cold excitations from the non-Franck-Condon region of the ground electronic state to the two components of the lowest 2 E1 g state split by Jahn-Teller distortion. The weak DIBs at 9428 and 9365 Å are assigned to the first vibronic transitions involving the low-energy vibrational modes and components of the lowest 2 E1 g electronic state.

*Biochemistry ; 57(23): 3244-3251, 2018 06 12.*

**| MEDLINE**| ID: mdl-29489337

##### RESUMO

Lactate racemase (LarA) of Lactobacillus plantarum contains a novel organometallic cofactor with nickel coordinated to a covalently tethered pincer ligand, pyridinium-3-thioamide-5-thiocarboxylic acid mononucleotide, but its function in the enzyme mechanism has not been elucidated. This study presents direct evidence that the nickel-pincer cofactor facilitates a proton-coupled hydride transfer (PCHT) mechanism during LarA-catalyzed lactate racemization. No signal was detected by electron paramagnetic resonance spectroscopy for LarA in the absence or presence of substrate, consistent with a +2 metal oxidation state and inconsistent with a previously proposed proton-coupled electron transfer mechanism. Pyruvate, the predicted intermediate for a PCHT mechanism, was observed in quenched solutions of LarA. A normal substrate kinetic isotope effect ( kH/ kD of 3.11 ± 0.17) was established using 2-α-2H-lactate, further supporting a PCHT mechanism. UV-visible spectroscopy revealed a lactate-induced perturbation of the cofactor spectrum, notably increasing the absorbance at 340 nm, and demonstrated an interaction of the cofactor with the inhibitor sulfite. A crystal structure of LarA provided greater resolution (2.4 Å) than previously reported and revealed sulfite binding to the pyridinium C4 atom of the reduced pincer cofactor, mimicking hydride reduction during a PCHT catalytic cycle. Finally, computational modeling supports hydride transfer to the cofactor at the C4 position or to the nickel atom, but with formation of a nickel-hydride species requiring dissociation of the His200 metal ligand. In aggregate, these studies provide compelling evidence that the nickel-pincer cofactor acts by a PCHT mechanism.

##### Assuntos

Proteínas de Bactérias/química , Coenzimas/química , Lactobacillus plantarum/enzimologia , Níquel/química , Compostos Organometálicos/química , Prótons , Racemases e Epimerases/química , Proteínas de Bactérias/genética , Coenzimas/genética , Coenzimas/metabolismo , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Lactobacillus plantarum/genética , Níquel/metabolismo , Compostos Organometálicos/metabolismo , Domínios Proteicos , Racemases e Epimerases/genética , Espectrofotometria Ultravioleta*J Phys Chem A ; 122(13): 3480-3488, 2018 Apr 05.*

**| MEDLINE**| ID: mdl-29533626

##### RESUMO

Accurate prediction of the intersystem crossing rates is important for many different applications in chemistry, physics, and biology. Recently, we implemented the ab initio multiple spawning (AIMS) molecular dynamics method to describe the intersystem crossing processes, where nonradiative transitions between electronic states with different spin multiplicities are mediated by spin-orbit coupling. Our original implementation of the direct AIMS dynamics used the complete active space self-consistent field (CASSCF) method to describe multiple coupled electronic states on which multidimensional Gaussian wave packets were propagated. In this work, we improve the computational efficiency and versatility of the AIMS dynamics by interfacing it with the density functional theory (DFT). The new AIMS-DFT and the earlier AIMS-CASSCF implementations are used to investigate the effects of electronic structure methods on the predicted intersystem crossing rate constants and the lowest triplet state lifetime in the GeH2 molecule. We also compare the rates and lifetimes obtained from the AIMS simulations with those predicted by the statistical nonadiabatic transition state theory (NA-TST). In NA-TST, the probabilities of spin transitions are calculated using the Landau-Zener, weak coupling, and Zhu-Nakamura formulas. Convergence of the AIMS rate constants with respect to the simulation time and the number of initial trajectories (Gaussian wave packets) is analyzed. An excellent agreement between AIMS-DFT and AIMS-CASSCF can be explained by cancelation of two effects: higher energy barriers and a stronger spin-orbit coupling in DFT relative to CASSCF. The rate constants obtained with the AIMS-DFT dynamics are about a factor of 2 larger than those predicted by the statistical NA-TST. This is likely due to the importance of the nonlocal interstate transitions missing from the NA-TST description.

*J Chem Phys ; 147(12): 124304, 2017 Sep 28.*

**| MEDLINE**| ID: mdl-28964028

##### RESUMO

We investigate the lifetimes of vibrational states of diatomic alkali-alkaline-earth cations to determine their suitability for ultracold experiments where long decoherence time and controllability by an external electric field are desirable. The potential energy and permanent dipole moment curves for the ground electronic states of LiBe+, LiMg+, NaBe+, and NaMg+ are obtained using the coupled cluster with singles doubles and triples and multireference configuration interaction methods in combination with large all-electron cc-pCVQZ and aug-cc-pCV5Z basis sets. The energies and wave functions of all vibrational states are obtained by solving the Schrödinger equation for nuclei with the B-spline basis set method. To predict the lifetimes of vibrational states, the transition dipole moments, as well as the Einstein coefficients describing spontaneous emission, and the stimulated absorption and emission induced by black body radiation are calculated. Surprisingly, in all studied ions, the lifetimes of the highest excited vibrational states are similar to the lifetimes of the ground vibrational states indicating that highly vibrationally excited ions could be useful for the ultracold experiments requiring long decoherence time.

*J Am Chem Soc ; 139(37): 13102-13109, 2017 09 20.*

**| MEDLINE**| ID: mdl-28829125

##### RESUMO

Herein we describe the synthesis, structure, and properties of chiral peropyrenes. Using p-terphenyl-2,2â³,6,6â³-tetrayne derivatives as precursors, chiral peropyrenes were formed after a 4-fold alkyne cyclization reaction promoted by triflic acid. Due to the repulsion of the two aryl substituents within the same bay region, the chiral peropyrene adopts a twisted backbone with an end-to-end twist angle of 28° that was unambiguously confirmed by X-ray crystallographic analysis. The chiral peropyrene products absorb and emit in the green region of the UV-visible spectrum. Circular dichroism spectroscopy shows strong Cotton effects (ΔÎµ = ±100 M-1 cm-1 at 300 nm). The Raman data shows the expected D-band along with a split G-band that is due to longitudinal and transversal G modes. This data corresponds well with the simulated Raman spectra of chiral peropyrenes. The chiral peropyrene products also display circularly polarized luminescence. The cyclization reaction mechanism and the enantiomeric composition of the peropyrene products are explained using DFT calculations. The inversion barrier for racemization was determined experimentally to be 29 kcal/mol and is supported by quantum mechanical calculations.

*J Phys Chem A ; 120(43): 8691-8698, 2016 Nov 03.*

**| MEDLINE**| ID: mdl-27739682

##### RESUMO

Rubredoxin is a small iron-sulfur protein involved in biological electron transfer, which is accomplished by changing the oxidation state of the iron atom in the active site. We investigate the possibility of spin-forbidden transitions between the lowest energy electronic states with different spin multiplicities in the rubredoxin active site models [Fe(SCH3)4]n (n = 2-, 1-, 0) using nonadiabatic transition state theory (NA-TST). The equilibrium structures, minimum energy crossing point structures and Hessians were obtained with density functional theory. The spin-orbit coupling (SOC) was calculated with the complete active space configuration interaction method using the two-electron spin-orbit Breit-Pauli Hamiltonian. We found several crossings between the lowest energy spin states associated with the changes in Fe coordination. However, only triplet/quintet crossings in [Fe(SCH3)4]2- and [Fe(SCH3)4]0, as well as a quartet/sextet crossing in [Fe(SCH3)4]- are characterized by nonzero first-order SOC responsible for transitions between these spin states. The rates of spin-forbidden transitions in the [Fe(SCH3)4]2- complex are 1 and 2 orders of magnitude higher than the rates in the [Fe(SCH3)4]- and [Fe(SCH3)4]0 complexes, respectively. These rate differences are related to a large variation of the SOC between the complexes with different charges, which in turn comes from different molecular orbitals involved in the spin-flip transitions. Finally, we demonstrate that the differences between the NA-TST rates and the rates calculated under the assumption of completely spin-allowed transitions could be as large as 4 orders of magnitude. This means that even in qualitative discussions of the reaction mechanisms involving changes in spin states the partially spin-forbidden nature of the transitions between these states must be taken into account.

##### Assuntos

Rubredoxinas/química , Rubredoxinas/metabolismo , Domínio Catalítico , Elétrons , Ferro/química , Modelos Moleculares*J Phys Chem A ; 120(18): 2911-9, 2016 05 12.*

**| MEDLINE**| ID: mdl-27064356

##### RESUMO

Dynamics at intersystem crossings are fundamental to many processes in chemistry, physics, and biology. The ab initio multiple spawning (AIMS) method was originally developed to describe internal conversion dynamics at conical intersections where derivative coupling is responsible for nonadiabatic transitions between electronic states with the same spin multiplicity. Here, the applicability of the AIMS method is extended to intersystem crossing dynamics in which transitions between electronic states with different spin multiplicities are mediated by relativistic spin-orbit coupling. In the direct AIMS dynamics, the nuclear wave function is expanded in the basis of frozen multidimensional Gaussians propagating on the coupled electronic potential energy surfaces calculated on the fly. The AIMS method for intersystem crossing is used to describe the nonadiabatic transitions between the (3)B1 and (1)A1 states of GeH2. The potential energies and gradients were obtained at the CASSCF(6,6)/6-31G(d) level of theory. The spin-orbit coupling matrix elements were calculated with the configuration interaction method using the two-electron Breit-Pauli Hamiltonian. The excited (3)B1 state lifetime and intersystem crossing rate constants were estimated by fitting the AIMS state population with the first-order kinetics equation for a reversible unimolecular reaction. The obtained rate constants are compared with the values predicted by the statistical nonadiabatic transition state theory with transition probabilities calculated using the Landau-Zener and weak coupling formulas.

*J Phys Chem A ; 119(8): 1332-8, 2015 Feb 26.*

**| MEDLINE**| ID: mdl-25635385

##### RESUMO

The ability of time-independent nonadiabatic transition state theory (NA-TST) to reproduce intersystem crossing dynamics obtained from the more computationally demanding Tully fewest switches trajectory surface hopping method is investigated. The two approaches are applied to the intersystem crossing between the ground (1)A1 state and lowest energy (3)B1 state of SiH2, coupled through the spin-orbit interaction. For NA-TST, the transition probabilities are calculated using the Landau-Zener formula and the Delos formula which accounts for tunneling. The fewest switches method produces rate constants of 7.6 × 10(11) s(-1) for the triplet to singlet transition and 5.2 × 10(11) s(-1) for the singlet to triplet transition, using a first-order kinetics model. This corresponds to a triplet electronic state lifetime of 781 fs. The NA-TST predicted rate constants are 1-2 orders of magnitude smaller, leading to a larger triplet state lifetime, as compared with the fewest switches method. This discrepancy cannot be explained by the difference in transition probabilities obtained from NA-TST and fewest switches molecular dynamics, and it is believed to be a result of the NA-TST semilocal description of nonadiabatic transitions in the vicinity of the intersystem crossing. Also, the larger triplet state lifetime obtained from NA-TST could be a result of the quantum sampling of rovibrational states, which is missing in classical trajectories traversing the crossing seam.

*J Phys Chem A ; 119(6): 1066-73, 2015 Feb 12.*

**| MEDLINE**| ID: mdl-25603170

##### RESUMO

We investigate the effect of H2 binding on the spin-forbidden nonadiabatic transition probability between the lowest energy singlet and triplet electronic states of [NiFe]-hydrogenase active site model, using a velocity averaged Landau-Zener theory. Density functional and multireference perturbation theories were used to provide parameters for the Landau-Zener calculations. It was found that variation of the torsion angle between the terminal thiolate ligands around the Ni center induces an intersystem crossing between the lowest energy singlet and triplet electronic states in the bare active site and in the active site with bound H2. Potential energy curves between the singlet and triplet minima along the torsion angle and H2 binding energies to the two spin states were calculated. Upon H2 binding to the active site, there is a decrease in the torsion angle at the minimum energy crossing point between the singlet and triplet states. The probability of nonadiabatic transitions at temperatures between 270 and 370 K ranges from 35% to 32% for the active site with bound H2 and from 42% to 38% for the bare active site, thus indicating the importance of spin-forbidden nonadiabatic pathways for H2 binding on the [NiFe]-hydrogenase active site.

##### Assuntos

Hidrogênio/química , Hidrogenase/química , Domínio Catalítico , Hidrogênio/metabolismo , Hidrogenase/metabolismo , Teoria Quântica*J Phys Chem A ; 118(46): 10902-8, 2014 Nov 20.*

**| MEDLINE**| ID: mdl-25329724

##### RESUMO

This work presents a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane, using the ab initio multiple spawning (AIMS) program that has been interfaced with the General Atomic and Molecular Electronic Structure System (GAMESS) quantum chemistry package for on-the-fly electronic structure evaluation. The interface strategy is discussed, and the capabilities of the combined programs are demonstrated with a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane. Energies, gradients, and nonadiabatic coupling matrix elements were obtained with the state-averaged complete active space self-consistent field method, as implemented in GAMESS. The influence of initial vibrational excitation on the outcome of the photoinduced isomerization is explored. Increased vibrational excitation in the CNNC torsional mode shortens the excited state lifetime. Depending on the degree of vibrational excitation, the excited state lifetime varies from â¼60-200 fs. These short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.

*J Chem Phys ; 140(18): 184315, 2014 May 14.*

**| MEDLINE**| ID: mdl-24832278

##### RESUMO

We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X(1)Σ(+) electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-Î¶ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-Î¶ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtaining the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm(-1) for LiNa and by no more than 114 cm(-1) for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm(-1), and the discrepancies for the anharmonic correction are less than 0.1 cm(-1). We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.

*Angew Chem Int Ed Engl ; 51(51): 12795-800, 2012 Dec 14.*

**| MEDLINE**| ID: mdl-23065934

*J Chem Phys ; 132(5): 054103, 2010 Feb 07.*

**| MEDLINE**| ID: mdl-20136301

##### RESUMO

We introduce a geminal-augmented multiconfigurational self-consistent field method for describing electron correlation effects. The approach is based on variational optimization of a MCSCF-type wave function augmented by a single geminal. This wave function is able to account for some dynamic correlation without explicit excitations to virtual molecular orbitals. Test calculations on two-electron systems demonstrate the ability of the proposed method to describe ionic and covalent electronic states in a balanced way, i.e., including the effects of both static and dynamic correlation simultaneously. Extension of the theory to larger systems will potentially provide an alternative to standard multireference methods.

*J Chem Phys ; 128(24): 241101, 2008 Jun 28.*

**| MEDLINE**| ID: mdl-18601308

##### RESUMO

We generalize the Poisson equation to attenuated Newtonian potentials. If the attenuation is at least exponential, the equation provides a local mapping between the density and its potential. We use this to derive several density functionals for the short-range self-interaction energy.

*J Chem Phys ; 128(20): 201104, 2008 May 28.*

**| MEDLINE**| ID: mdl-18513003

##### RESUMO

We discuss a generalization of the resolution of the identity by considering one-body resolutions of two-body operators, with particular emphasis on the Coulomb operator. We introduce a set of functions that are orthonormal with respect to 1r(12) and propose that the resulting "resolution of the Coulomb operator," r(12) (-1)=mid R:phi(i)phi(i)mid R:, may be useful for the treatment of large systems due to the separation of two-body interactions. We validate our approach by using it to compute the Coulomb energy of large systems of point charges.

*J Chem Phys ; 120(11): 5169-75, 2004 Mar 15.*

**| MEDLINE**| ID: mdl-15267387

##### RESUMO

This work presents a study of reactions between neutral and negatively charged Au(n) clusters (n=2,3) and molecular hydrogen. The binding energies of the first and second hydrogen molecule to the gold clusters were determined using density functional theory (DFT), second order perturbation theory (MP2) and coupled cluster (CCSD(T)) methods. It is found that molecular hydrogen easily binds to neutral Au(2) and Au(3) clusters with binding energies of 0.55 eV and 0.71 eV, respectively. The barriers to H(2) dissociation on these clusters with respect to Au(n)H(2) complexes are 1.10 eV and 0.59 eV for n=2 and 3. Although negatively charged Au(n) (-) clusters do not bind molecular hydrogen, H(2) dissociation can occur with energy barriers of 0.93 eV for Au(2) (-) and 1.39 eV for Au(3) (-). The energies of the Au(2)H(2) (-) and Au(3)H(2) (-) complexes with dissociated hydrogen molecules are lower than the energies of Au(2) (-)+H(2) and Au(3) (-)+H(2) by 0.49 eV and 0.96 eV, respectively. There is satisfactory agreement between the DFT and CCSD(T) results for binding energies, but the agreement is not as good for barrier heights.