Theoretical studies on structures and electronic spectra of linear carbon chains C2nH+ (n = 1−5)

The density functional theory (DFT) and the complete active space self‐consistent‐field (CASSCF) method have been used for full geometry optimization of carbon chains C_2nH⁺ (n = 1–5) in their ground states and selected excited states, respectively. Calculations show that C_2nH⁺ (n = 1–5) have stable linear structures with the ground state of X³Π for C₂H⁺ or X³Σ^? for other species. The excited‐state properties of C_2nH⁺ have been investigated by the multiconfigurational second‐order perturbation theory (CASPT2), and predicted vertical excitation energies show good agreement with the available experimental values. On the basis of our calculations, the unsolved observed bands in previous experiments have been interpreted. CASSCF/CASPT2 calculations also have been used to explore the vertical emission energy of selected low‐lying states in C_2nH⁺ (n = 1–5). Present results indicate that the predicted vertical excitation and emission energies of C_2nH⁺ have similar size dependences, and they gradually decrease as the chain size increases. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

UV‐photoexcitation and ultrafast dynamics of HCFC‐132b (CF2ClCH2Cl)

The UV‐induced photochemistry of HCFC‐132b (CF₂ClCH₂Cl) was investigated by computing excited‐state properties with time‐dependent density functional theory (TDDFT), multiconfigurational second‐order perturbation theory (CASPT2), and coupled cluster with singles, doubles, and perturbative triples (CCSD(T)). Excited states calculated with TDDFT show good agreement with CASPT2 and CCSD(T) results, correctly predicting the main excited‐states properties. Simulations of ultrafast nonadiabatic dynamics in the gas phase were performed, taking into account 25 electronic states at TDDFT level starting in two different spectral windows (8.5 ± 0.25 and 10.0 ± 0.25 eV). Experimental data measured at 123.6 nm (10 eV) is in very good agreement with our simulations. The excited‐state lifetimes are 106 and 191 fs for the 8.5 and 10.0 eV spectral windows, respectively. Internal conversion to the ground state occurred through several different reaction pathways with different products, where 2Cl, C‐Cl bond breakage, and HCl are the main photochemical pathways in the low‐excitation region, representing 95% of all processes. On the other hand, HCl, HF, and C‐Cl bond breakage are the main reaction pathways in the higher excitation region, with 77% of the total yield. © 2015 Wiley Periodicals, Inc.     

CASPT2 study on low‐lying states of HBN and HNB radicals

In this study, some low‐lying states of the HBN and HNB radicals have been studied using multiconfiguration second‐order perturbation theory. The geometries of all stationary points along the potential energy surfaces (PESs) were optimized at the CASPT2/cc‐pVQZ level. The ground and the first excited states of HBN were predicted to be X²Π and A²Σ⁺ states, respectively. It was predicted that the ground state of HNB is X²Σ⁺ state. The A²Π state of HNB has unique imaginary frequency, which was different from the previously published results. A bending local minimum M1 was found for the first time along the 1²A″ PES, and the A²Π state of HNB should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves (PECs) of isomerization reactions for HBN ? HNB were calculated as a function of HBN bond angle. By comparing the CASPT2 and CASSCF calculated results, we concluded that the influence of the dynamic electron correlation on HBN ? HNB system is not large. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Initial excited‐state relaxation of locked retinal protonated schiff base chromophore. An insight from coupled cluster and multireference perturbation theory calculations

The initial S₁ excited‐state relaxation of retinal protonated Schiff base (RPSB) analog with central C11C12 double bond locked by eight‐membered ring (locked‐11.8) was investigated by means of multireference perturbation theory methods (XMCQDPT2, XMS‐CASPT2, MS‐CASPT2) as well as single‐reference coupled‐cluster CC2 method. The analysis of XMCQDPT2‐based geometries reveals rather weak coupling between in‐plane and out‐of‐plane structural evolution and minor energetical relaxation of three locked‐11.8 conformers. Therefore, a strong coupling between bonds length inversion and backbone out‐of‐plane deformation resulting in a very steep S₁ energy profile predicted by CASSCF/CASPT2 calculations is in clear contradiction with the reference XMCQDPT2 results. Even though CC2 method predicts good quality ground‐state structures, the excited‐state structures display more advanced torsional deformation leading to ca. 0.2 eV exaggerated energy relaxation and significantly red shifted (0.4–0.7 eV) emission maxima. According to our findings, the initial photoisomerization process in locked‐11.8, and possibly in other RPSB analogs, studied fully (both geometries and energies) by multireference perturbation theory may be somewhat slower than predicted by CASSCF/CASPT2 or CC2 methods. © 2018 Wiley Periodicals, Inc.     

Theoretical study on HBC− and HCB− anions using multiconfiguration second‐order perturbation theory

The HBC^? and HCB^? anions have been studied using the complete active space self‐consistent field, CASPT2, and DFT/B3LYP methods with the contracted atomic natural orbital (ANO) and cc‐pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO and B3LYP/cc‐pVTZ levels. The ground state of HBC^? is predicted to be X²? state, which is different from the previously published results. The CASPT2/ANO potential energy curves (PECs) of isomerization reactions were calculated as a function of HBC bond angle and the PECs also show the ²? state is the ground state of HBC^? anion. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Photophysics of Schiff Bases: Theoretical Study of Salicylidene Methylamine

The proton‐transfer reaction in a model aromatic Schiff base, salicylidene methylamine (SMA), in the ground and in the lowest electronically‐excited singlet states, is theoretically analyzed with the aid of second‐order approximate coupled‐cluster model CC2, time‐dependent density functional theory (TD‐DFT) using the Becke, three‐parameter Lee–Yang–Parr (B3LYP) functional, and complete active space perturbation theory CASPT2 electronic structure methods. Computed vertical‐absorption spectra for the stable ground‐state isomers of SMA fully confirm the photochromism of SMA. The potential‐energy profiles of the ground and the lowest excited singlet state are calculated and four photophysically relevant isomeric forms of SMA; α, β, γ, and δ are discussed. The calculations indicate two S₁/S₀ conical intersections which provide non‐adiabatic gates for a radiationless decay to the ground state. The photophysical scheme which emerges from the theoretical study is related to recent experimental results obtained for SMA and its derivatives in the low‐temperature argon matrices (J. Grzegorzek, A. Filarowski, Z. Mielke, Phys. Chem. Chem. Phys. 2011 , 13, 16596–16605). Our results suggest that aromatic Schiff bases are potential candidates for optically driven molecular switches.     

Theoretical study on low‐lying states of HAlO+ and HOAl+ cations

Some low‐lying states of HAlO⁺ and HOAl⁺ cations have been studied using the complete‐active‐space self‐consistent field (CASSCF) and multiconfiguration second‐order perturbation theory (CASPT2) methods with the contracted atomic natural orbital (ANO) basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO and CASPT2/ANO levels. The ground and the first excited states of HAlO⁺ are predicted to be X²Π and A²Σ⁺ states, respectively. It was predicted that the ground state of HOAl⁺ is X²Σ⁺ state. The A²Π state of HOAl⁺ has unique imaginary frequency. A bent local minimum M1 was found along the 1²A″ potential energy surface, and the A²Π state of HOAl⁺ should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves of isomerization reactions were calculated as a function of HAlO bond angle. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

The Role of the nπ* 1Au State in the Photoabsorption and Relaxation of Pyrazine

The geometric, energetic, and spectroscopic properties of the ground state and the lowest four singlet excited states of pyrazine have been studied by using DFT/TD‐DFT, CASSCF, CASPT2, and related quantum chemical calculations. The second singlet nπ* state, ¹A_u, which is conventionally regarded dark due to the dipole‐forbidden ¹A_u←¹A_g transition, has been investigated in detail. Our new simulation has shown that the state could be visible in the absorption spectrum by intensity borrowing from neighboring nπ* ¹B_3u and ππ* ¹B_2u states through vibronic coupling. The scans on potential‐energy surfaces further indicated that the ¹A_u state intersects with the ¹B_2u states near the equilibrium of the latter, thus implying its participation in the ultrafast relaxation process.     

CASPT2 study on low‐lying states of HMgO and HOMg

The HMgO and magnesium monohydroxide (HOMg) have been reinvestigated using the complete active space self‐consistent field (CASSCF) and multiconfiguration second‐order perturbation theory (CASPT2) methods with the contracted atomic natural orbital (ANO) basis sets. The geometries of all stationary points along the potential energy surfaces (PESs) were optimized at the CASSCF/ANO levels. The ground and the first excited states of HMgO are predicted to be X²Π and A²Σ⁺ states, respectively. It was predicted that the ground state of HOMg is X²Σ⁺ state. The A²Π state of HOMg has unique imaginary frequency. A bent local minimum M1 was found for the first time along the 1²A″ PES and the A²Π state of HOMg should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves of isomerization reactions were calculated as a function of HMgO bond angle. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Approach to the atmospheric chemistry of methyl nitrate and methylperoxy nitrite. Chemical mechanisms of their formation and decomposition reactions in the gas phase

Potential energy surfaces, minimum energy reaction paths, minima, transition states, reaction barriers, and conical intersections for the most important atmospheric reactions of methyl nitrate (CH(3)ONO(2)) and methylperoxy nitrite (C(3)HOONO) on the electronic ground state have been studied (i) with the second-order multiconfigurational perturbation theory (CASPT2) by computation of numerical energy gradients for stationary points and (ii) with the density functional theory (DFT). The proposed mechanism explains the conversion of unreactive alkyl peroxy radicals into alkoxy radicals: CH(3)O(2) + NO <=> CH(3)OONO <=> CH(3)O + NO(2) left arrow over right arrow CH(3)ONO(2). Additionally, several discrepancies found in the comparison of the results obtained from the two employed approaches are analyzed. CASPT2 predicts that all dissociation reactions into radicals occur without an extra exit energy barrier. In contrast, DFT finds transition states for the dissociations of cis- and trans-methylperoxy nitrite into CH(3)O + NO(2). Furthermore, multiconfigurational methods [CASPT2 and complete active space SCF (CAS-SCF)] predict the isomerization of CH3ONO2 to CH3OONO to occur in a two-step mechanism: (i) CH(3)ONO(2) --> CH(3)O + NO(2); and (ii) CH(3)O + NO(2) --> CH(3)OONO. The reason for this has to do with the coupling of the ground electronic state with the first excited state. Therefore, it is demonstrated that DFT methods based on single determinantal wave functions give an incorrect picture of the aforementioned reaction mechanisms.     

Theoretical prediction on HAlS+ and HSAl+ cations using multiconfiguration second‐order perturbation theory

Some low‐lying states of the HAlS⁺ and HSAl⁺ cations have been studied for the first time by large‐scale theoretical calculations using three methods: complete active space self‐consistent field (CASSCF), complete active second‐order perturbation theory (CASPT2), and density functional theory Becke's three‐parameter hybrid function with the nonlocal correlation of Lee–Yang–Parr (B3LYP) with the contracted atomic natural orbital (ANO‐L) and cc‐pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces (PESs) were optimized at the CASSCF/ANO‐L and B3LYP/cc‐pVTZ levels. The ground and the first excited states of linear HAlS⁺ are predicted to be X²Π and A²Σ⁺ states, respectively. For the linear HSAl⁺ structure, the first excited state is A²Σ⁺. The X²Π state of linear HSAl⁺ is a second‐order saddle point, because it has two imaginary frequencies. Two bent global minima M1 and M2 were found along the 1²A′ and 1²A″ PESs, respectively. The CASPT2/ANO‐L potential energy curves of isomerization reactions were calculated as a function of HAlS bond angle. According to our calculations, the ground‐state HAlS⁺ is linear, whereas the ground‐state HSAl⁺ is bent. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

The Low‐Lying Excited States of 2,2′‐Bithiophene: A Theoretical Analysis

The low‐energy regions of the singlet→singlet, singlet→triplet, and triplet→triplet electronic spectra of 2,2′‐bithiophene are studied using multiconfigurational second‐order perturbation theory (CASPT2) and extended atomic natural orbitals (ANO) basis sets. The computed vertical, adiabatic, and emission transition energies are in agreement with the available experimental data. The two lowest singlet excited states, 1¹B_u and 2¹B_u, are computed to be degenerate, a novel feature of the system to be borne in mind during the rationalization of its photophysics. As regards the observed high triplet quantum yield of the molecule, it is concluded that the triplet states 2³A_g and 2³B_u, separated about 0.4 eV from the two lowest singlet excited states, can be populated by intersystem crossing from nonplanar singlet states.     

Ruthenocene and cyclopentadienyl pyrrolyl ruthenium as precursors for ruthenium atomic layer deposition: a comparative study of dissociation enthalpies

RuCp₂ (ruthenocene) and RuCpPy (cyclopentadienyl pyrrolyl ruthenium) complexes are used in ruthenium (Ru) atomic layer deposition (ALD) but exhibit a markedly different reactivity with respect to the substrate and co-reactant. In search of an explanation, we report here the results of a comparative study of the heterolytic and homolytic dissociation enthalpy of these two ruthenium complexes, making use of either density functional theory (DFT) or multiconfigurational perturbation theory (CASPT2). While both methods predict distinctly different absolute dissociation enthalpies, they agree on the relative values between both molecules. A reduced heterolytic dissociation enthalpy is obtained for RuCpPy compared to RuCp₂, although the difference obtained from CASPT2 (19.9?kcal/mol) is slightly larger than the one obtained with any of the DFT functionals (around 17?kcal/mol). Both methods also agree on the more pronounced stability of the Cp^? ligand in RuCpPy than in RuCp₂ (by around 9?kcal/mol with DFT and by 6?kcal/mol with CASPT2).     

Theoretical study of the vertical electron affinity and ionization potentials of C3

The electron affinity and first three ionization potentials of C₃ are calculated using the multiconfigurational SCF and configuration interaction methods and by Möller-Plesset perturbation theory. Whereas Koopmans' theorem and SCF calculations indicate that the first cation state is ²Π_u, upon inclusion of correlation effects both the ²Σ_u and ²Σ_g cation states are found to lie lower in energy. CI calculations indicate that the ground state (²Π_g) anion is stable by 1.74 eV. Allowing for the error in the calculated electron affinity of the carbon atom, C₃^? is estimated to be stable by 2.0 eV, in excellent agreement with the 2.05 eV value determined from recent photodetachment measurements. No excited anion states are found to be bound at the equilibrium geometry of the neutral molecule.     

Electronic structures of NbGen−/0/+ (n = 1–3) clusters from multiconfigurational CASPT2 and density matrix renormalization group-CASPT2 calculations

Density functional theory and multiconfigurational CASPT2 and density matrix renormalization group DMRG-CASPT2 have been employed to study the low-lying states of NbGe_n^−/0/+ (n = 1–3) clusters. With the DMRG-CASPT2 method, the active spaces are extended to a size of 20 orbitals. For most of the states, the CASPT2 relative energies are comparable with the DMRG-CASPT2 results. The leading configuration, bond distances, vibrational frequencies, and relative energies of the low-lying states of these clusters were calculated. The ground states of these clusters were computed to be ³Δ, ⁴Φ, and ⁵Φ of NbGe^−/0/+; ³A₂, ⁴B₁, and ³B₁ of cyclic-NbGe₂^−/0/+; and ¹A′, 1²A″ and 1²A′′ (²E), and ³A″ of tetrahedral-NbGe₃^−/0/+ isomers. For NbGe cluster, our calculations proposed that the ⁶∑ is almost degenerate with the ⁴Φ with the CASPT2 and DMRG-CASPT2 relative energies of 0.05 and 0.06 eV. The adiabatic detachment energies of NbGe_n⁻ (n = 1–3) clusters were estimated to be 1.46, 1.55, and 2.18 eV by the CASPT2 method. The relevant detachment energies of the anionic ground state and the ionization energies of the neutral ground states are evaluated at the CASPT2 level.     

Theoretical prediction on HBeN− and HNBe− anions using multiconfiguration second‐order perturbation theory

The HBeN^? and HNBe^? anions have been investigated for the first time using the CASSCF, CASPT2, and DFT/B3LYP methods with the contracted atomic natural orbital (ANO) and cc‐pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO and B3LYP/cc‐pVTZ levels. The ground and the first excited states of HBeN^? are predicted to be X²Π and A²Σ⁺ states, respectively. It was predicted that the ground state of HNBe^? is X²Σ⁺ state. The A²Π state of HNBe^? has unique imaginary frequency. A bend local minimum M1 was found along the 1²A″ potential energy surface and the A²Π state of HNBe^? should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves of isomerization reactions were calculated as a function of HBeN bond angle. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Ab initio calculations for the potential curves and spin–orbit coupling of Mg2

 The ground state and several low-lying excited states of the Mg₂ dimer have been studied by means of a combination of the complete-active-space multiconfiguration self-consistent-field (CASSCF)/CAS multireference second-order perturbation theory (CASPT2) method and coupled-cluster with single and double excitations and perturbative contribution of connected triple excitations [CCSD(T)] scheme. Reasonably good agreement with experiment has been obtained for the CCSD(T) ground-state potential curve but the dissociation energy of the only experimentally known A¹Σ _u ⁺ excited state of Mg₂ is somewhat overestimated at the CASSCF/CASPT2 level. The spectroscopic constants D _e, R _e and ω_e deduced from the calculated potential curves for other states are also reported. In addition, some spin–orbit matrix elements between the excited singlet and triplet states of Mg₂ have been evaluated as a function of internuclear separation. Received: 10 May 2001 / Accepted: 15 August 2001 / Published online: 30 October 2001     

Theoretical Study of Remote Substituent Effects on X-H （X=CH2, NH,O） Bond Dissociation Energies of Azulene

In the study, the X-H （X=CH2, NH, O） bond dissociation energies （BDE） of para-substituted azulene （Y-C10H8X-H） were predicted theoretically for the first time using Density Functronal Theory （DFT） methods at UB3LYP/6-311 ＋ ＋g（2df,2p）//UB3LYP/6-31 ＋g（d） level. It was found that the substituents exerted similar effects on the X-H BDE of azulene as those on benzene, except for 6-substituted 2-methylazulene. Owing to the substituent-dipole interaction, the reaction constants （ρ^＋） of 2- and 6-Y-CIoHsX-H （X=NH and O only） varied violently. The origin of the substituent effects on the X-H BDE of azulene was found, by both GE/RE and SIE theory, to be directly associated with variation of the radical effects, although the ground effects also played a modest role in determining the net. substituent effects.     

A MS-CASPT2 study of the low-lying electronic excited states of CH2BrCl

The low-lying singlet excited states of CH₂BrCl have been calculated using multiconfigurational CASSCF, second-order perturbation theory CASPT2 and its multistate extension MS-CASPT2. The CASSCF method shows spurious valence–Rydberg mixing and a wrong order of states. Inclusion of dynamical correlation by single root CASPT2 lowers dramatically the energy of the valences states but does not lead to a complete separation between valence and Rydberg states. This situation is improved by the MS-CASPT2 calculations, which gives two valence states for both A^′ and A″ symmetries below the lowest Rydberg state, corresponding to n(Br)→σ^*(C–Br) and n(Cl)→σ^*(C–Cl) transitions at 6.1 eV (203 nm) and 7.2 eV (173 nm), and being repulsive along C–Br and C–Cl coordinates.