Electronic structure of guanidine and its derivatives from X-ray photoelectron spectroscopy and density functional theory studies

Electronic structure of guanidine, diphenylguanidine, their protonated forms, and guanidinium chloride have been studied by X-ray photoelectron spectroscopy and quantum-chemical modeling. From the derived geometry parameters and electronic structure, the effect of protonation on localization of the electron density has been revealed. The lines in the valence region of the X-ray photoelectron spectra have been assigned.     

Application of the dressed time-dependent density functional theory for the excited states of linear polyenes

Dressed Time-Dependent Density Functional Theory (Maitra et al., J Chem Phys 2004, 120, 5932) is applied to selected linear polyenes. Limits of validity of the approximation are briefly discussed. The implementation strategy is described. Results for the 2(1)B(u) and 2(1)A(g) states of selected linear polyenes are presented and compared with accessible experimental and theoretical results.     

Vibronic coupling and double excitations in linear response time-dependent density functional calculations: dipole-allowed states of N2

The present study serves two purposes. First, we evaluate the ability of present time-dependent density functional response theory (TDDFRT) methods to deal with avoided crossings, i.e., vibronic coupling effects. In the second place, taking the vibronic coupling effects into account enables us, by comparison to the configuration analysis in a recent ab initio study [J. Chem. Phys. 115, 6438 (2001)], to identify the neglect of double excitations as the prime cause of limited accuracy of these linear response based TDDFRT calculations for specific states. The "statistical averaging of (model) orbital potentials (SAOP)" Kohn-Sham potential is used together with the standard adiabatic local-density approximation (ALDA) for the exchange-correlation kernel. We use the N2 molecule as prototype, since the TDDFRT/SAOP calculations have already been shown to be accurate for the vertical excitations, while this molecule has a well-studied, intricate vibronic structure as well as significant double excitation nature in the lowest 1Pi(u) state at elongated bond lengths. A simple diabatizing scheme is employed to obtain a diabatic potential energy matrix, from which we obtain the absorption spectrum of N2 including vibronic coupling effects. Considering the six lowest dipole allowed transitions of 1Sigma(u)+ and 1Pi(u) symmetry, we observe a good general agreement and conclude that avoided crossings and vibronic coupling can indeed be treated satisfactorily on the basis of TDDFRT excitation energies. However, there is one state for which the accuracy of TDDFRT/ALDA clearly breaks down. This is the state for which the ab initio calculations find significant double excitation character. To deal with double excitation character is an important challenge for time-dependent density functional theory.     

Analysis of vibrational spectra of 5,6-dimethyl benzimidazole based on density functional theory calculations

The vibrational spectra of 5,6-dimethyl benzimidazole (5,6DBZ) have been computed using the standard B3LYP/6-311G** method and basis set combinations. The solid phase FT-IR and FT-Raman spectra were recorded in the region 4000-400 and 3500-100 cm(-1), respectively. A close agreement was achieved between the observed and calculated frequencies by employing normal coordinate calculations. The observed and simulated spectra were found to be well comparable.     

Improving the predictive quality of time-dependent density functional theory calculations of the X-ray emission spectroscopy of organic molecules

The simulation of X-ray emission spectra of organic molecules using time-dependent density functional theory (TDDFT) is explored. TDDFT calculations using standard hybrid exchange-correlation functionals in conjunction with large basis sets can predict accurate X-ray emission spectra provided an energy shift is applied to align the spectra with experiment. The relaxation of the orbitals in the intermediate state is an important factor, and neglect of this relaxation leads to considerably poorer predicted spectra. A short-range corrected functional is found to give emission energies that required a relatively small energy shift to align with experiment. However, increasing the amount of Hartree–Fock exchange in this functional to remove the need for any energy shift led to a deterioration in the quality of the calculated spectral profile. To predict accurate spectra without reference to experimental measurements, we use the CAM-B3LYP functional with the energy scale determined with reference to a Δself-consistent field calculation for the highest energy emission transition.     

Structure, spectroscopy, and reactivity properties of porphyrin pincers: a conceptual density functional theory and time-dependent density functional theory study

Porphyrin and pincer complexes are both important categories of compounds in biological and catalytic systems. The idea to combine them is computationally investigated in this work. By employment of density functional theory (DFT), conceptual DFT, and time-dependent DFT approaches, structure, spectroscopy, and reactivity properties of porphyrin pincers are systematically studied for a selection of divalent metal ions. We found that the porphyrin pincers are structurally and spectroscopically different from their precursors and are more reactive in electrophilic and nucleophilic reactions. A few quantitative linear/exponential relationships have been discovered between bonding interactions, charge distributions, and DFT chemical reactivity indices. These results are implicative in chemical modification of hemoproteins and understanding chemical reactivity in heme-containing and other biologically important complexes and cofactors.     

Exploring odd-even effects of simple oligomer-like DRCNnT series: a study based on density functional theory/time-dependent density functional theory calculations

Odd-even effects of short-circuit current density and power conversion efficiency (PCE) are an interesting phenomenon in some organic solar cells. Although some explanations have been given, why they behave in such a way is still an open question. In the present work, we investigate a set of acceptor-donor-acceptor simple oligomer-like small molecules, named the DRCNnT (n = 5-9) series, to give an insight into this phenomenon because the solar cells based on them have high PCE (up to 10.08%) and show strong odd-even effects in experiments. By modeling the DRCNnT series and using density functional theory, we have studied the ground-state electronic structures of the DRCNnT (n = 5-9) series in condensed phase. The calculated results reproduce the experimental trends well. Furthermore, we find that the exciton-binding energies of the DRCNnT series may be one of the key parameters to explain this phenomenon because they also show odd-even effects. In addition, by studying the effects of alkyl branch and terminal group on odd-even effects of dipole moment, we find that eliminating one or two alkyl branches does not break the odd-even effects of dipole moments, but eliminating one or two terminal groups does. Finally, we conclude that removing one alkyl branch close to the terminal group of DRCN5T can decrease highest occupied molecular orbital (HOMO) energy (thus increasing open circuit voltage) and increase dipole moment (thus enhancing charge separation and short-circuit current). This could be a new and simple method to increase the PCE of DRCN5T-based solar cells.     

Electronic structure and optical properties of charged oligofluorenes studied by VIS/NIR spectroscopy and time-dependent density functional theory

The electronic structure and optical properties of charged oligofluorenes were studied experimentally and theoretically. Measurements of the optical absorption spectra of charged oligofluorenes in dilute solutions have been performed by using the pulse radiolysis technique. In addition, optical absorption spectra of radical cations and anions in a solid matrix were measured after gamma-irradiation at 77 K. The optical absorption spectra were measured in the range of 440-2100 nm (0.6-2.8 eV) and compared with results from time-dependent density functional theory (TDDFT) calculations. The calculated charge induced deformations and charge distribution do not indicate the occurrence of polaronic effects. The potential energy profiles for rotation around the inter-unit bond show that oligofluorenes are nonplanar in their neutral state, while they tend to more planar structures in their charged state. The optical absorption spectra of charged oligofluorenes are dependent on the angle between neighboring units. TDDFT absorption energies shift to lower values with increasing chain length, which suggests that the charge delocalizes along the oligomer chain.     

Excited electron-bubble states in superfluid 4He: a time-dependent density functional approach

We present a systematic study on the excited electron-bubble states in superfluid (4)He using a time-dependent density functional approach. For the evolution of the 1P bubble state, two different functionals accompanied with two different time-development schemes are used, namely an accurate finite-range functional for helium with an adiabatic approximation for electron versus an efficient zero-range functional for helium with a real-time evolution for electron. We make a detailed comparison between the quantitative results obtained from the two methods, which allow us to employ with confidence the optimal method for suitable problems. Based on this knowledge, we use the finite-range functional to calculate the time-resolved absorption spectrum of the 1P bubble, which in principle can be experimentally determined, and we use the zero-range functional to real-time evolve the 2P bubble for several hundreds of picoseconds, which is theoretically interesting due to the break down of adiabaticity for this state. Our results discard the physical realization of relaxed, metastable configurations above the 1P state.     

Accurate evaluation of valence and low-lying Rydberg states with standard time-dependent density functional theory

Using a standard exchange-correlation functional, namely, PBE0, the basis set dependence of time-dependent density functional theory (TD-DFT) calculations has been explored using 33 different bases and five organic molecules as test cases. The results obtained show that this functional can provide accurate (i.e., at convergence) results for both valence and low-lying Rydberg excitations if at least one diffuse function for the heavy atoms is included in the basis set. Furthermore, these results are in fairly good agreement with the experimental data and with those delivered by other functionals specifically designed to yield correct asymptotic/long-range behavior. More generally, the PBE0 calculations show that a greater accuracy can be obtained for both Rydberg and valence excitations if they occur at energies below the epsilonHOMO + 1 eV threshold. This latter value is proposed as a thumb rule to verify the accuracy of TD-DFT/PBE0 applications.     

Molecular and vibrational structure of tetroxo d0 metal complexes in their excited states. a study based on time-dependent density functional calculations and Franck-Condon theory

We have applied time dependent density functional theory to study excited state structures of the tetroxo d(0) transition metal complexes MnO(4)(-), TcO(4)(-), RuO(4), and OsO(4). The excited state geometry optimization was based on a newly implemented scheme [Seth et al. Theor. Chem. Acc. 2011, 129, 331]. The first excited state has a C(3v) geometry for all investigated complexes and is due to a "charge transfer" transition from the oxygen based HOMO to the metal based LUMO. The second excited state can uniformly be characterized by "charge transfer" from the oxygen HOMO-1 to the metal LUMO with a D(2d) geometry for TcO(4)(-), RuO(4), and OsO(4) and two C(2v) geometries for MnO(4)(-). It is finally found that the third excited state of MnO(4)(-) representing the HOMO to metal based LUMO+1 orbital transition has a D(2d) geometry. On the basis of the calculated excited state structures and vibrational modes, the Franck-Condon method was used to simulate the vibronic structure of the absorption spectra for the tetroxo d(0) transition metal complexes. The Franck-Condon scheme seems to reproduce the salient features of the experimental spectra as well as the simulated vibronic structure for MnO(4)(-) generated from an alternative scheme [Neugebauer J. J. Phys. Chem. A 2005, 109, 1168] that does not apply the Franck-Condon approximation.     

Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. II. Calculation of A terms

The magnetically perturbed time-dependent density functional theory is used to derive equations for the magnetic circular dichroism (MCD) of degenerate transitions of closed shell molecules. The MCD of this type of transition can be divided into two contributions. The dominant contribution is usually that from A terms that arise because of the breaking of the degeneracy of the excited state in the presence of the magnetic field. The second contribution comes from B terms that arise because of the perturbation of the transition dipole by the magnetic field. The formalism is applied to ten tetrahedral d(0) transition metal oxy- and thioanions. The MCD parameters of these systems are reproduced quite well by the calculations. Simulated spectra derived from the calculated parameters are in good agreement with the observed spectra.     

Calculation of static and dynamic linear magnetic response in approximate time-dependent density functional theory

We report implementations and results of time-dependent density functional calculations (i) of the frequency-dependent magnetic dipole-magnetic dipole polarizability, (ii) of the (observable) translationally invariant linear magnetic response, and (iii) of a linear intensity differential (LID) which includes the dynamic dipole magnetizability. The density functional calculations utilized density fitting. For achieving gauge-origin independence we have employed time-periodic magnetic-field-dependent basis functions as well as the dipole velocity gauge, and have included explicit density-fit related derivatives of the Coulomb potential. We present the results of calculations of static and dynamic magnetic dipole-magnetic dipole polarizabilities for a set of small molecules, the LID for the SF6 molecule, and dispersion curves for M-hexahelicene of the origin invariant linear magnetic response as well as of three dynamic polarizabilities: magnetic dipole-magnetic dipole, electric dipole-electric dipole, and electric dipole-magnetic dipole. We have also performed comparison of the linear magnetic response and magnetic dipole-magnetic dipole polarizability over a wide range of frequencies for H2O and SF6.     

Density matrix based time-dependent density functional theory and the solution of its linear response in real time domain

A density matrix based time-dependent density functional theory is extended in the present work. Chebyshev expansion is introduced to propagate the linear response of the reduced single-electron density matrix upon the application of a time-domain delta-type external potential. The Chebyshev expansion method is more efficient and accurate than the previous fourth-order Runge-Kutta method and removes a numerical divergence problem. The discrete Fourier transformation and filter diagonalization of the first-order dipole moment are implemented to determine the excited state energies. It is found that the filter diagonalization leads to highly accurate values for the excited state energies. Finally, the density matrix based time-dependent density functional is generalized to calculate the energies of singlet-triplet excitations.     

Theoretical studies on electronic spectroscopy and dynamics with the real-time time-dependent density functional theory

Time-dependent density functional theory (TDDFT) has evolved into a general routine to extract the energies of low-lying excited states over the last decades. Driven by the remarkable progress of laser technology, the study of the interaction between matter and intense laser fields with ultrashort pulse duration develops rapidly. A great number of new strong field phenomena emerge. The requirement of a theoretical tool to study the intense field phenomena and dynamical processes of polyatomic systems is urgent. To extend the power of the TDDFT beyond the linear responses, an alternative scheme has been developed by numerically solving the time-dependent Kohn-Sham equations directly in real-time domain. In this article, we summarize the algorithms and capabilities of the real-time TDDFTon studying electron spectroscopy and dynamics of polyatomic systems. The failure of TDDFT with the adiabatic localdensity approximation on some dynamical processes and the possible solutions are synopsized as well. The numerical implementation of algorithms and applications of RT-TDDFT on the linear and nonlinear spectroscopies and electronic dynamics of nano-size nonmetal clusters are displayed.     

Analytical Hessian of electronic excited states in time-dependent density functional theory with Tamm-Dancoff approximation

We present the analytical expression and computer implementation for the second-order energy derivatives of the electronic excited state with respect to the nuclear coordinates in the time-dependent density functional theory (TDDFT) with Gaussian atomic orbital basis sets. Here, the Tamm-Dancoff approximation to the full TDDFT is adopted, and therefore the formulation process of TDDFT excited-state Hessian is similar to that of configuration interaction singles (CIS) Hessian. However, due to the replacement of the Hartree-Fock exchange integrals in CIS with the exchange-correlation kernels in TDDFT, many quantitative changes in the derived equations are arisen. The replacement also causes additional technical difficulties associated with the calculation of a large number of multiple-order functional derivatives with respect to the density variables and the nuclear coordinates. Numerical tests on a set of test molecules are performed. The simulated excited-state vibrational frequencies by the analytical Hessian approach are compared with those computed by CIS and the finite-difference method. It is found that the analytical Hessian method is superior to the finite-difference method in terms of the computational accuracy and efficiency. The numerical differentiation can be difficult due to root flipping for excited states that are close in energy. TDDFT yields more exact excited-state vibrational frequencies than CIS, which usually overestimates the values.     

Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)4] cluster: a density functional theory/time-dependent density functional theory investigation

We present a combined density functional theory (DFT)/time-dependent density functional theory (TDDFT) study of the geometry, electronic structure, and absorption and emission properties of the tetranuclear "cubane" Cu4I4py4 (py = pyridine) system. The geometry of the singlet ground state and of the two lowest triplet states of the title complex were optimized, followed by TDDFT excited-state calculations. This procedure allowed us to characterize the nature of the excited states involved in the absorption spectrum and those responsible for the dual emission bands observed for this complex. In agreement with earlier experimental proposals, we find that while in absorption the halide-to-pyridine charge-transfer excited state (XLCT*) has a lower energy than the cluster-centered excited state (CC*), a strong geometrical relaxation on the triplet cluster-centered state surface leads to a reverse order of the excited states in emission.     

Electronic photodissociation spectroscopy of Aun- x Xe (n = 7-11) versus time-dependent density functional theory prediction

Electronic (one-photon) photodepletion spectra were recorded for gold cluster anions complexed with one xenon atom over the photon energy range 2.1-3.4 eV. Clusters were generated by pulsed laser vaporization and probed under collisionless molecular beam conditions. The spectra obtained are highly structured with the narrowest features--assigned to individual electronic transitions--having bandwidths of less than 40 meV. Time-dependent density functional theory predictions of optically allowed transitions for the most stable--planar--isomers of the corresponding bare metal cluster anions are generally consistent with the experimental observation.     

Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism: calculation of B terms

Magnetically perturbed time-dependent density functional theory is applied to the calculation of the magnetic circular dichroism (MCD) B terms of closed shell molecules. Two approaches to evaluating B term parameters are described: a sum-over-states-type approach and an approach based on the direct solution of the matrix equations. The advantages and disadvantages and technical challenges of each approach are described. The interpretation of the parameters in terms of ground and excited state perturbations are discussed. Several applications of the methodology are described. Calculations of the MCD of ethene are used to compare the sum-over-states and direct solution approaches and to illustrate the potential for analysis. The other applications involving azabenzes, sulfur-nitrogen heterocycles and quinone molecules are compared with experiment and other theoretical calculations. For the most part, all important features of the observed spectra are reproduced.