STEREOELECTRONIC PROPERTIES OF PHOTOSYNTHETIC AND RELATED SYSTEMS — V. AB INITIO CONFIGURATION INTERACTION CALCULATIONS ON THE GROUND AND LOWER EXCITED SINGLET AND TRIPLET STATES OF ETHYL CHLOROPHYLLIDE a AND ETHYL PHEOPHORBIDE a

Abstract— Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying excited singlet and triplet states of ethyl pheophorbide a (Et-Pheo a) and ethyl chlorophyllide a (Et-Chl a), and are employed in an analysis of the electronic absorption spectra of these systems. In both molecules the visible spectrum is found to consist of transitions to the two lowest-lying ¹(π, π*) states, S₁ and S₂. The configurational compositions of S₁ and S₂ in both molecules are similar, and are described qualitatively in terms of a four-orbital model. The S₁← S₀ transition in each case is predicted to be intense, and is largely in-plane y-polarized, while the S₂← S₀ transition is predicted to be extremely weak and in-plane polarized. The orientation of the S₂← S₀ transition dipole is not conclusively established in the present calculations. The Soret band in both molecules is composed of transitions to no less than ten states (S_3-S₁₂ in Et-Chl a and S₃-S₇S₉-S₁₂. and S₁₄ in Et-Pheo a), which exhibit primarily (π, π*) character. The configurational compositions of these states are generally a complex mixture of excitations from both occupied macrocyclic π molecular orbitals and occupied orbitals with electron density in the cyclopen-tanone ring and the carbomethoxy chain. No clear correspondences are evident between respective Soret states of the two systems. Transitions to these states are generally intense and display a variety of in-plane polarizations. Two additional Soret states of Et-Pheo a, S₈ and S₁₃, exhibit primarily (n. π*) character. S₈ is characterized by excitations from u and non-bonding regions of the carbomethoxy chain, while S₁₃ is described by n →π* excitations involving the nitrogen atom of ring II. No corresponding (n, π*) states were found for Et-Chl a. In both molecules the lowest two triplet states, T₁ and T₂, are found to lie lower in energy than S₁. while T, and S₁ are approximately degenerate. The configurational compositions of T₁-T₄ of both molecules are nearly identical, and may be described by a four-orbital model. However, the compositions of T₁-T₄ differ sharply from those of S₁ and S₂. A number of higher-lying ³(π, π*) states of both molecules (T₅-T₁₃ in Et-Chi a and T₈-T₉, T₁₁-T₁₃ in Et-Pheo a) are found to have energies similar to the singlet Soret states, relative to S₀. They are characterized by a complex mixture of configurations which do not include significant contributions involving the four-orbital model. In addition, two ³(n, π*) states of Et-Pheo a, T₁₀ and T₁₄, are found, which are somewhat analogous to S₈ and S₁₃. Additional data presented include the charge distributions and molecular dipole moments of the S₀. S₁, and T₁ states of both molecules, as well as energies and oscillator strengths of computed S_n←S₁ and T_n←₁ transitions.     

Electronic Structure of Silver Oxides Investigated by AgL XANES Spectroscopy

The chemistry of binary and multinary silver oxides spans from subvalent species (with a mean oxidation number for Ag smaller than + 1) to compounds with Ag in high oxidation states as + 2 and + 3. We have investigated a range of silver oxides, including the binary compounds Ag₂O, AgO, Ag₃O₄ and Ag₂O₃ as well as subvalent ternary oxides, by AgL₃ and AgL₁ XANES spectroscopy. The different valence states of silver are clearly reflected in AgL₃ and AgL₁ XANES spectra. The method thus allows the determination of average oxidation numbers. In addition, the degree of electronic interaction (localized or delocalized electronic states) in silver‐oxygen compounds can be estimated on the basis of AgL₃ XANES spectra.     

Inverting the external-potential-to-electron density map in systems of electrons by minimization of a least-squares fit functional for analytic potentials

In a system of electrons, there is a map connecting any external potential v with its electron density ρ _v. In this work, we describe a procedure for inverting this potential-to-density map, so that potentials (if any) corresponding to a target density ρ_t can be obtained. We give the trial external potential v _α , an analytic expression depending on a number of parameters α = (α₁, …) and then minimize the least-squares integral ∫(ρ _α − ρ_t)² d r by the conjugate gradient method, where ρ _α is the density corresponding to v _α . The implementation takes advantage of the analytic nature of v _α . The procedure can be applied to any system and quantum chemistry model, and works both for ground and excited states, as well as for ensembles of states. The method is tested with some excited states of the particle-in-a-box model, confirming the lack of a Hohenberg–Kohn theorem for excited states. It is also applied to the first singlet excited state of the helium atom, where, apart from the nucleus–electron attraction potential, some generalized external potentials are found.     

Mechanism of vibrational relaxation and intersystem crossing within excited ion-pair states of I2

Visible and ultraviolet fluorescence of I₂, following excitation by ArF/193nm excimer laser pulses, was recorded for different pressures of argon buffer gas in a flow system. Dispersed fluorescence spectra due to the transitionsD’(2_g) → A’(2_y andD(0 _n ⁺ )→X0 _g ⁺ ) were analysed by inversion and spectral simulations. Thus vibrational distributions in the emitting states were obtained as a function of pressure to determine the mechanism of relaxation to populate the lowest quantum levels of theD’ state, which are the emitting states in the iodine laser. Fast intersystem crossing is found to occur from initially populated vibrational levels of theD state to other ion-pair states correlating with the ground state ions, followed by rapid relaxation, involving both direct vibrational relaxation within individual states and intersystem crossing between states.     

Triplet excited states of nitronaphthalenes. IV. 1,2- and 1,8-dinitronaphthalenes

Nanosecond flash photolysis of 1,2- and 1,8-dinitronaphthalenes (1,2-DNO₂N; 1,8-DNO₂N) in nonpolar and polar solvents shows transient species with absorption maxima and lifetimes dependent on solvent polarity. In deaerated n-hexane the absorption maxima and lifetimes (1/K) are 490 nm and 1.0 μsec for 1,2-DNO₂N and 550 nm and 2.5 μsec for 1,8-DNO₂N. In deaerated ethanol the corresponding values are 550 nm and 4.3 μsec for 1,2-DNO₂N and 590 nm and 5.3 μsec for 1,8-DNO₂N. The transient absorptions are attributed to the lowest triplet excited states T₁ of the 1,2- and 1,8-DNO₂N. The observed red shifts in the absorption maxima of the T₁ states are indicative of the extent to which electronic charge is transferred intramolecularly during the T₁ → T_n transitions. Furthermore, the increased lifetime of the T₁ states with increasing solvent polarity indicates the intramolecular charge transfer character of the T₁ states. Changes of dipole moments accompanying the T₁ → T_n transitions as well as rate constants for electron or proton transfer and hydrogen abstraction reactions involving the T₁ states of 1,2- and 1,8-DNO₂N and tributyl tin hydride (Bu₃SnH) as the hydrogen donor were determined together with the activation energy of the hydrogen abstraction reaction for the case of 1,2-DNO₂N. The spectroscopic and kinetic data obtained in this work demonstrate that the triplet states of 1,2- and 1,8-DNO₂N behave like n → π* states in nonpolar media while in polar solvents the n → π* character of these states is reduced with a simultaneous increase in their intramolecular charge transfer character.     

Multiple-State Emissions from Neat,Single-Component Molecular Solids: Suppression of Kasha's Rule

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3′H-[1,1′-biisobenzofuranylidene]-3,3′-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3′H-[1,1′-bibenzo[c] thiophenylidene]-3,3′-dione, are found to fluoresce in their neat solid phases, from upper (S₂) and lowest (S₁) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S₂ and S₁ states (T₂ and T₁ states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S₂ excited states (phosphorescence from T₂ excited states). These results, including unprecedented fluorescence quantum yields (2.3–9.6 %) from the S₂ states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by “suppressing” Kasha's rule.     

Unoccupied titanium 3d states due to subcluster formation in stoichiometric TiO2 nanoparticles

The source of unoccupied Ti 3d states in the case of stoichiometric anatase structured (TiO₂)_n clusters has been investigated using ab initio methods. These unoccupied gap states appear for example in the case of a stoichiometric (TiO₂)₃₈ cluster. We show that the origin of these gap states is related to effective subcluster formation which gives rise to empty defect‐like gap states, when these states are split off from conduction band. © 2015 Wiley Periodicals, Inc.     

Theoretical electronic structure of the molecule ScI

Theoretical investigation of the 18 lowest electronic states of the molecule ScI in the representation ^2S+1Λ^(±) has been performed via CASSCF and MRCI (single and double excitation with Davidson correction) calculations. To the best of our knowledge these calculated electronic states are the first ones from ab initio methods. Thirteen electronic states between 4,500 cm^?1 and 21,000 cm^?1 have been studied for the first time and have not yet been observed experimentally. The harmonic frequency ω_e, the internuclear distance R_e, the electronic transition energy with respect to the ground state T_e, and the rotational constant B_e have been calculated for the considered electronic states. By using the canonical functions approach the eigenvalues E_υ and the rotational constants B_υ have also been calculated for the six lowest‐lying electronic states. The comparison of these results with the theoretical and the experimental data available in the literature shows a good agreement. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Multiple‐State Emissions from Neat,Single‐Component Molecular Solids: Suppression of Kasha's Rule

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)‐3H,3′H‐[1,1′‐biisobenzofuranylidene]‐3,3′‐dione, (E)‐3‐(3‐oxobenzo[c] thiophen‐1(3H)‐ylidene)isobenzofuran‐1(3H)‐one, and (E)‐3H,3′H‐[1,1′‐bibenzo[c] thiophenylidene]‐3,3′‐dione, are found to fluoresce in their neat solid phases, from upper (S₂) and lowest (S₁) singlet excited states, even at room temperature in air. Photophysical studies, single‐crystal structures, and theoretical calculations indicate that large energy gaps between S₂ and S₁ states (T₂ and T₁ states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S₂ excited states (phosphorescence from T₂ excited states). These results, including unprecedented fluorescence quantum yields (2.3–9.6 %) from the S₂ states in the neat solids, establish a unique molecular skeleton for achieving multi‐colored emissions from upper excited states by “suppressing” Kasha's rule.     

Ab initio study of low-lying electronic states of the FNO2 molecule

Ab initio electronic structure calculations are reported for low-lying electronic states, ¹A₁, ¹A₂, ³A₂, ¹B₁, ³B₁, ¹B₂, and ³B₂ of the FNO₂ molecule. Geometric parameters for the ground state ¹A₁ are predicted by MRSDCI calculations with a double-zeta plus polarization basis set. The vertical excitation energies for these electronic states are determined using MRSDCI/DZ+P calculations at the ground-state equilibrium conformation. The oscillator strengths and radiative lifetimes for some electronic states are calculated based on the MRSDCI wave functions. © 1993 John Wiley & Sons, Inc.     

One-Electron Pseudo-Potential Determination of Stable Isomers of the Li*Ar n Excited Clusters: Absorption Spectra

We present pseudo-potential calculations of geometrical structures of stable isomers of LiAr _n clusters with both an electronic ground state and excited states of the lithium atom. The Li atom is perturbed by argon atoms in LiAr _n clusters. Its electronic structure obtained as the eigenfunctions of a single-electron operator describing the electron in the field of a Li⁺Ar _n core, the Li⁺ and Ar atoms are replaced by pseudo-potentials. These pseudo-potentials include core-polarization operators to account for the polarization and correlation of the inert core with the valence Lithium electron [J Chem Phys 116, 1839 1]. The geometry optimization of the ground and excited states of LiAr _n (n = 1–12) clusters is carried out via the Basin-Hopping method of Wales et al. [J Phys Chem 101, 5111 2; J Chem Phys 285, 1368 3]. The geometries of the ground and ionic states of LiAr _n clusters were used to determine the energy of the high excited states of the neutral LiAr _n clusters. The variation of the excited state energies of LiAr _n clusters as a function of the number of argon atoms shows an approximate Rydberg character, corresponding to the picture of an excited electron surrounding an ionic cluster core, is already reached for the 3s state. The result of optical transitions calculations shows that the absorption spectral features are sensitive to isomer structure. It is clearly the case for transitions close to the 2p levels of Li which are distorted by the cluster environment.     

Molecular electric properties in electronic excited states: multipole moments and polarizabilities of H2O in the lowest1 B 1 and3 B 1 excited states

Summary The dipole and quadrupole moments and the dipole polarizability tensor components are calculated for the¹ B ₁ and³ B ₁ excited states of the water molecule by using the complete active space (CAS) SCF method and an extended basis set of atomic natural orbitals. The dipole moment in the lowest¹ B ₁ (0.640 a.u.) and³ B ₁ (0.416 a.u.) states is found to be antiparallel to that in the ground electronic state of H₂O. The shape of the quadrupole moment ellipsoid is significantly modified by the electronic excitation to both states investigated in this paper. All components of the excited state dipole polarizability tensor increase by about an order of magnitude compared to their values in the ground electronic state. The present results are used to discuss some aspects of intermolecular interactions involving molecules in their excited electronic states.     

Potential energy surfaces of pseudoaromatic molecules: An MMVB and CASSCF study of pentalene

The S₀ and S₁ potential energy surfaces of pentalene were studied using MMVB—a hybrid force-field/parametrized valence bond (VB) method designed to simulate CASSCF calculations for ground and covalent excited states. The results were calibrated against full CASSCF calculations. Four distinct critical points were optimized: on S₀, a C_2h minimum (with alternating single and double bonds) and a D_2h transition structure; and on S₁, a D_2h minimum and an adjacent S₁/S₀ conical intersection. A VB exchange density matrix (which is independent of the choice of the spin-coupled basis) was used to rationalize the S₀ and S₁ surface topologies. Craig defined pseudoaromatic molecules to be those with nontotally symmetric electronic ground states. For pentalene, this is true for both CASSCF and MMVB calculations: the CASSCF S₀ transition structure is an open-shell B_1x singlet, and the VB ground state is dominated by a spin-coupling which transforms as B_1g. A C_2v minimum and a D_2h transition structure were located on the CASSCF S₂ potential energy surface. This state cannot be represented by MMVB because of the importance of ionic configurations. The characters of the S₁ S₂ states of pentalene are shown to be reverse of the S₁ and S₂ states of benzene. © 1996 John Wiley & Sons, Inc.     

High-Resolution Experimental Study on Photodissocaition of N2O

We study the photodissociation dynamics of nitrous oxide using the time-sliced ion velocity imaging technique at three photolysis wavelengths of 134.20, 135.30, and 136.43 nm. The O(¹S_J=0)+N₂(X¹∑_g⁺) product channels were investigated by measuring images of the O(¹S_J=0) products. Vibrational states of N₂(X¹∑_g⁺) products were fully resolved in the images. Product total kinetic energy releases (TKER) and the branching ratios of vibrational states of N₂ products were determined. It is found that the most populated vibrational states of N₂ products are v=2 and v=3. The angular anisotropy parameters (β values) were also derived. The β values are very close to 2 at low vibrational states of the correlated N₂(X¹∑_g⁺) products at all three photolysis wavelengths, and gradually decrease to about 1.4 at v=7. This indicates the dissociation is mainly through a parallel transition state to form products at lower vibrational states, and the highly vibrational exited products are from a more bent configuration. This is consistent with the observed shift of the most intense rotational structure in the TKER as the vibrational quantum number increases.     

Thermodynamic Quantities and Defect Structure of La0.6Sr0.4Co1−yFeyO3−δ(y=0–0.6) from High-Temperature Coulometric Titration Experiments

The partial energies and entropies of O₂in perovskite-type oxides La_0.6Sr_0.4Co_1−yFe_yO_3−δ(y=0, 0.1, 0.25, 0.4, 0.6) were determined as a function of nonstoichiometryδby coulometric titration of oxygen in the temperature range 650–950°C. An absolute reference value ofδwas obtained by thermogravimetry in air. The nonstoichiometry at a given oxygen pressure and temperature decreases with iron contenty. At low nonstoichiometries the oxygen chemical potential decreases withδ. The observed behavior can be interpreted by assuming random distribution of oxygen vacancies, an electronic structure with both localized donor states on Fe, and a partially filled itinerant electron band, of which the density of states at the Fermi level scales with the Co content. The energy of the Fe states is close to the energy at the Fermi level in the conduction band. The observed trends of the thermodynamic quantities can be interpreted in terms of the itinerant electron model only when the iron content is small. At high values ofδthe chemical potential of O₂becomes constant, indicating partial decomposition of the perovskite phase. The maximum value ofδat which the compositions are single-phase increases with temperature.     

Tamm states in zigzag carbon nanotubes: Analytic estimates in the Hückel approximation

The frontier molecular orbitals of [C _n ] _q hydrocarbons, fragments of (n, 0) nanotubes, were considered. Asymptotic estimates for two different sets of frontier molecular orbitals were obtained in the Hückel approximation. The problem was shown to be equivalent to the search for model polyene levels with alternating resonance parameters (β and β′ = γβ). The γ parameter was determined by the symmetry type of molecular orbitals and took on values from 0 to 2. The problem was reduced to an analysis of a regular linear polyene with a modified terminal atom by taking alternant symmetry into account. The states of the system were classified according to quasi-momentum Θ values, which could be complex. Solutions with a complex Θ value were localized at tube ends and could be interpreted as Tamm states. The criterion of the appearance of Tamm solutions for the problem under consideration was formulated, γ < 1 − 1/(q + 2). The conclusion was drawn that these states for an arbitrary [C _n ] _q fragment lied close to the Fermi level, and their energies were described by the asymptotic equation α ± βρ^{(q + 1)}. Delocalized levels were always situated farther from the Fermi level than Tamm states.     

Anab initio quantum-chemical study of proton addition to F-, Ch3-, and CF3-substituted ethylene derivatives

Protonated forms of the molecules of ethylene derivatives with the general formula C₂X₂Y₂ (X=Y=H) (1), F (2), CH₃ (3) CH₃ (4); X=F, Y=H:cis-(5)trans- (6)) were calculated by theab initio MP2/6-31 G^* method with full geometry optimization. The minima and saddle points located on the potential energy surface (PES) of the protonated ethylene molecule correspond to the stationary states and transition states of proton migration, respectively. The stationary states are characterized by a nonclassical geometry of carbocations similar to that of π-complexes, whereas the transition states have a classical structure. Unlike1, the carbocations of molecules2–6 have the classical structure. The saddle points on the PES of the ethylene derivatives correspond to the structures of the π-complex type, which are the transition states of proton migration between the C atoms of the ethylene bond. The barrier to rotation about, the C−C bond depends essentially on the substituent nature. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1333–1337, August, 2000.     

Exploring the potential energy hypersurface of histamine monocation: Tautomerism in gas phase

The potential energy hypersurface of the histamine monocation is determined by ab initio methods at the STO -4G level using analytical gradient techniques. Three transition states and two minima have been found for the N_τ? H tautomer. One of the transition states connects the trans conformational region with a minimum gauche structure, where the proton of the ammonium group is approximately halfway between the N_π of the imidazole group and the N of the ammonium group, but nearer to the N_π. This minimum connects the potential energy surface of the N_τ? H tautomer with the imidazolium one. In the latter region, three transition states and two minima have been found. Critical points are discussed in relation with experimental data and histamine H₂ receptor models.