Ground State Potential Surface Research Articles

An accurate ground state potential surface for the scattering reaction F- + F2(v,j) → F2(v',j') + F.

The accuracy of three-dimensional adiabatic potential energies for F3− ions is reduced with higher level ab initio methods. The accurate numerically fitted method, the 3D-spline method, was performed to obtain an accurate adiabatic potential energy surface for the ground state of F3− ions. A linear minimum geometry was found in the present work, and the corresponding parameters were in excellent agreement with those of the optimized structure and those reported in previous work. By comparing the lowest potential energies for different attacking angles one can see that the favorite reaction pathway for the title reaction is F− + F2(v,j) → F3−(C∞) → F− + F2(v′,j′).

Simple Quantum Dynamics with Thermalization.

In this paper, we introduce two simple quantum dynamics methods. One is based on the popular surface-hopping method, and the other is based on rescaling of the propagation on the bath ground-state potential surface. The first method is special, as it avoids specific feedback from the simulated quantum system to the bath and can be applied for precalculated classical trajectories. It is based on the equipartition theorem to determine if hops between different potential energy surfaces are allowed. By comparing with the formally exact Hierarchical Equations Of Motion approach for four model systems we find that the method generally approximates the quantum dynamics toward thermal equilibrium very well. The second method is based on rescaling of the nonadiabatic coupling and also neglect the effect of the state of the quantum system on the bath. By the nature of the approximations, they cannot reproduce the effect of bath relaxation following excitation. However, the methods are both computationally more tractable than the conventional fewest switches surface hopping, and we foresee that the methods will be powerful for simulations of quantum dynamics in systems with complex bath dynamics, where the system–bath coupling is not too strong compared to the thermal energy.

Theoretical studies on cyclometalated platinum(II) complexes based on isoquinolinyl azolate: ππ-stacking interaction and photophysical properties

The photophysical properties of four Pt(II) complexes [Pt(Lx)2], x = 1–4, (1–4), where Lx are 6-t-butyl-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (1), 3,5-di-t-butyl-1-(3-trifluoromethyl-1H-pyrazol-5-yl) isoquinoline (2), 6-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (3), and 4-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (4), are investigated by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Furthermore, the binding interaction in Ptn stack is studied to discover the influence of different cyclometalated ligand. The calculated results rationalize that the complex 1 exhibits a stack of three molecules rather than the infinite aligned stack. Complexes 1 and 3 present the stronger tendency to form the aligned ππ-stacking interaction as compared with complexes 2 and 4. The dimers of other four complexes, 3a (Pt(L3)(Ma), Ma = 5-(2-pyridyl)-3-trifluoromethylpyrazole), 3b (Pt(L3)(Mb), Mb = 5-(4-phenyl-2-pyridyl)-3-trifluoromethylpyrazole), 3c (Pt(L3)(Mc), Mc = 5-(4-tert-butyl-2-pyridyl)-3-trifluoromethylpyrazole), and 5 (Pt(fppz)2 fppz = 5-(2-pyridyl)-3-trifluoromethylpyrazole), are also studied to investigate the effect of different aromatic ligand or substituents on the ππ-stacking interaction. The emissions of complexes 1–4 originate from various charge transfer states including the intraligand charge transfer (ILCT) and ligand-to-ligand charge transfer (LLCT) together with the metal-to-ligand charge transfer (MLCT). Finally, the items related with the radiative and nonradiative rate constants are examined. Besides the potential energy profile between the lowest triplet state (3MLCT) and metal centered state (3MC), the deactivation process of the 3MC state via the minimum energy crossing point (MECP) between the 3MC and the ground state (1S0) potential surfaces is also explored.

Excited-state wavepacket and potential reconstruction by coherent anti-Stokes Raman scattering

Among the major challenges in the chemical sciences is controlling chemical reactions and deciphering their mechanisms. Since much of chemistry occurs in excited electronic states, in the last three decades scientists have employed a wide variety of experimental techniques and theoretical methods to recover excited-state potential energy surfaces and the wavepackets that evolve on them. These methods have been partially successful but generally do not provide a complete reconstruction of either the excited state wavepacket or potential. We have recently proposed a methodology for reconstructing excited-state molecular wavepackets and the corresponding potential energy surface [Avisar and Tannor, Phys. Rev. Lett., 2011, 106, 170405]. In our approach, the wavepacket is represented as a superposition of the set of vibrational eigenfunctions of the molecular ground-state Hamiltonian. We assume that the multidimensional ground-state potential surface is known, and therefore these vibrational eigenfunctions are known as well. The time-dependent coefficients of the basis functions are obtained by experimental measurement of the resonant coherent anti-Stokes Raman scattering (CARS) signal. Our reconstruction strategy has several significant advantages: (1) the methodology requires no a priori knowledge of any excited-state potential. (2) It applies to dissociative as well as to bound excited-state potentials. (3) It is general for polyatomics. (4) The excited-state potential surface is reconstructed simultaneously with the wavepacket. Apart from making a general contribution to the field of excited-state spectroscopy, our method provides the information on the excited-state wavepacket and potential necessary to design laser pulse sequences to control photochemical reactions.

Correlation between excited-state intramolecular proton-transfer and singlet-oxygen quenching activities in 1-(acylamino)anthraquinones.

Excited-state intramolecular proton-transfer (ESIPT) and singlet-oxygen ((1)O2) quenching activities of intramolecularly hydrogen-bonded 1-(acylamino)anthraquinones have been studied by means of static and laser spectroscopies. The ESIPT shows a substituent effect, which can be explained in terms of the nodal-plane model. The ESIPT activity positively and linearly correlates with their (1)O2 quenching activity. The reason for this correlation can be understood by considering ESIPT-induced distortion of their ground-state potential surface and their encounter complex formation with (1)O2. Intramolecularly hydrogen-bonded hydroxyanthraquinones found in aloe also show a similar positive and linear correlation, which can be understood in the same way.

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

An accurate description of the complicated shape of the potential energy surface (PES) and that of the highly excited vibration states is of crucial importance for various unsolved issues in the spectroscopy and dynamics of ozone and remains a challenge for the theory. In this work a new analytical representation is proposed for the PES of the ground electronic state of the ozone molecule in the range covering the main potential well and the transition state towards the dissociation. This model accounts for particular features specific to the ozone PES for large variations of nuclear displacements along the minimum energy path. The impact of the shape of the PES near the transition state (existence of the "reef structure") on vibration energy levels was studied for the first time. The major purpose of this work was to provide accurate theoretical predictions for ozone vibrational band centres at the energy range near the dissociation threshold, which would be helpful for understanding the very complicated high-resolution spectra and its analyses currently in progress. Extended ab initio electronic structure calculations were carried out enabling the determination of the parameters of a minimum energy path PES model resulting in a new set of theoretical vibrational levels of ozone. A comparison with recent high-resolution spectroscopic data on the vibrational levels gives the root-mean-square deviations below 1 cm(-1) for ozone band centres up to 90% of the dissociation energy. New ab initio vibrational predictions represent a significant improvement with respect to all previously available calculations.

Predicting Singlet–Triplet Energy Splittings with Projected Hartree–Fock Methods

Hartree-Fock (HF) and density functional theory (DFT) methods are known for having problems in predicting singlet-triplet energy splittings when the system displays significant diradical character. Multireference methods are traditionally advocated to deal with the spin-contamination problem inherent in broken-symmetry mean-field methods. In the present work, spin-contamination is rigorously eliminated by means of a symmetry projection approach, carried out in a variation-after-projection fashion, recently implemented in our research group. We here explore the performance of a variety of projected Hartree-Fock (PHF) approaches (SUHF, KSUHF, SGHF, and KSGHF) in predicting singlet-triplet energy gaps in a broad set of diradical systems: small diatomic molecules, carbenes and silenes, and a few larger molecules (trimethylenemethane and benzyne isomers). For most of these systems, accurate experimental data is available in the literature. Additionally, we assess the quality of the geometrical parameters obtained in SUHF-based optimizations for some of the systems considered. Our results indicate that PHF methods yield high-quality multireference wave functions, providing a good description of the ground state potential surface as well as an accurate singlet-triplet splitting gap, all within a modest mean-field computational cost.

The Third Dimension of a More O'Ferrall-Jencks Diagram for Hydrogen Atom Transfer in the Isoelectronic Hydrogen Exchange Reactions of (PhX)(2)H(•) with X = O, NH, and CH(2).

A critical element in theoretical characterization of the mechanism of proton-coupled electron transfer (PCET) reactions, including hydrogen atom transfer (HAT), is the formulation of the electron and proton localized diabatic states, based on which a More O'Ferrall-Jencks diagram can be represented to determine the step-wise and concerted nature of the reaction. Although the More O'Ferrall-Jencks diabatic states have often been used empirically to develop theoretical models for PCET reactions, the potential energy surfaces for these states have never been determined directly based on first principles calculations using electronic structure theory. The difficulty is due to a lack of practical method to constrain electron and proton localized diabatic states in wave function or density functional theory calculations. Employing a multistate density functional theory (MSDFT), in which the electron and proton localized diabatic configurations are constructed through block-localization of Kohn-Sham orbitals, we show that distinction between concerted proton-electron transfer (CPET) and HAT, which are not distinguishable experimentally from phenomenological kinetic data, can be made by examining the third dimension of a More O'Ferrall-Jencks diagram that includes both the ground and excited state potential surfaces. In addition, we formulate a pair of effective two-state valence bond models to represent the CPET and HAT mechanisms. We found that the lower energy of the CPET and HAT effective diabatic states at the intersection point can be used as an energetic criterion to distinguish the two mechanisms. In the isoelectronic series of hydrogen exchange reaction in (PhX)(2)H(•), where X = O, NH, and CH(2), there is a continuous transition from a CPET mechanism for the phenoxy radical-phenol pair to a HAT process for benzyl radical and toluene, while the reaction between PhNH(2) and PhNH(•) has a mechanism intermediate of CPET and HAT. The electronically nonadiabatic nature of the CPET mechanism in the phenol system can be attributed to the overlap interactions between the ground and excited state surfaces, resulting in roughly orthogonal minimum energy paths on the adiabatic ground and excited state potential energy surfaces. On the other hand, the minimum energy path on the adiabatic ground state for the HAT mechanism coincides with that on the excited state, producing a large electronic coupling that separates the two surfaces by more than 120 kcal/mol.

UV protection and singlet-oxygen quenching activity of intramolecularly hydrogen-bonded hydroxyanthraquinone derivatives found in aloe

The UV protection and singlet-oxygen ( 1O 2) quenching activity of intramolecularly hydrogen-bonded hydroxyanthraquinone derivatives found in aloe have been studied by means of laser spectroscopy. The UV protective activity provided by excited-state intramolecular proton-transfer (ESIPT) in these molecules correlates with their 1O 2 quenching activity, and the UV protective molecules have high 1O 2-quenching function. The reason for this correlation can be understood by considering ESIPT-induced distortion of ground-state potential surfaces in encounter complexes with 1O 2.

Ion Imaging Study of NO3Radical Photodissociation Dynamics: Characterization of Multiple Reaction Pathways

The photodissociation of NO(3) has been studied using velocity map ion imaging. Measurements of the NO(2) + O channel reveal statistical branching ratios of the O((3)P(J)) fine-structure states, isotropic angular distributions, and low product translational energy consistent with barrierless dissociation along the ground state potential surface. There is clear evidence for two distinct pathways to the formation of NO + O(2) products. The dominant pathway (>70% yield) is characterized by vibrationally excited O(2)((3)Σ(g)(-), v = 5-10) and rotationally cold NO((2)Π), while the second pathway is characterized by O(2)((3)Σ(g)(-), v = 0-4) and rotationally hotter NO((2)Π) fragments. We speculate the first pathway has many similarities to the "roaming" dynamics recently implicated in several systems. The rotational angular momentum of the molecular fragments is positively correlated for this channel, suggesting geometric constraints in the dissociation. The second pathway results in almost exclusive formation of NO((2)Π, v = 0). Although product state correlations support dissociation via an as yet unidentified three-center transition state, theoretical confirmation is needed.

Extended permutation-inversion groups for simultaneous treatment of the rovibronic states of trans-acetylene, cis-acetylene, and vinylidene

The electronic ground state potential surface of acetylene (H C C H) has a minimum at the linear conformation, but the excited electronic states may have potential minima at a variety of nonlinear equilibrium shapes. This work is concerned with the group theoretical ideas necessary to treat simultaneously the symmetry properties of rovibronic states associated with three different planar acetylene equilibrium configurations, namely trans bent acetylene, cis bent acetylene, and vinylidene (H 2C C). We make use of three different kinds of groups: (i) point groups, (ii) permutation-inversion (PI) groups, and (iii) extended PI groups. The PI group is G 4 or G 8, depending on whether C H bond breaking is impossible (no bent acetylene ↔ vinylidene interconversion) or possible. The extended PI groups are G 4 ( 2 ) and G 8 ( 2 ) , respectively, when the only large amplitude motions are the CCH bends at each end of the molecule, and G 4 ( 8 ) and G 8 ( 8 ) , respectively, when internal rotation is added as a third large amplitude motion. Applied to acetylene, the results indicate that there will be no splittings of the rovibronic levels unless CH bond breaking occurs. Even without bond breaking, however, states of the cis and trans isomers just below their interconversion barrier will show “staggerings” in their K-structures, i.e., a given vibrational level will have three tunneling components at slightly different energies: one component will have levels with K = 4 n only (where n is an integer), a second component will have levels with K = 4 n + 2 only, and the third will have only odd- K levels. New experimental results for the S 1–cis electronic state of acetylene [21] are reviewed, and are found to be consistent with the group theory in so far as comparison is possible.

Cold chemistry with electronically excited Ca+ Coulomb crystals

Rate constants for chemical reactions of laser-cooled Ca(+) ions and neutral polar molecules (CH(3)F, CH(2)F(2), or CH(3)Cl) have been measured at low collision energies (<E(coll)>/k(B)=5-243 K). Low kinetic energy ensembles of (40)Ca(+) ions are prepared through Doppler laser cooling to form "Coulomb crystals" in which the ions form a latticelike arrangement in the trapping potential. The trapped ions react with translationally cold beams of polar molecules produced by a quadrupole guide velocity selector or with room-temperature gas admitted into the vacuum chamber. Imaging of the Ca(+) ion fluorescence allows the progress of the reaction to be monitored. Product ions are sympathetically cooled into the crystal structure and are unambiguously identified through resonance-excitation mass spectrometry using just two trapped ions. Variations of the laser-cooling parameters are shown to result in different steady-state populations of the electronic states of (40)Ca(+) involved in the laser-cooling cycle, and these are modeled by solving the optical Bloch equations for the eight-level system. Systematic variation of the steady-state populations over a series of reaction experiments allows the extraction of bimolecular rate constants for reactions of the ground state ((2)S(1/2)) and the combined excited states ((2)D(3/2) and (2)P(1/2)) of (40)Ca(+). These results are analyzed in the context of capture theories and ab initio electronic structure calculations of the reaction profiles. In each case, suppression of the ground state rate constant is explained by the presence of a submerged or real barrier on the ground state potential surface. Rate constants for the excited states are generally found to be in line with capture theories.

Electrophilic Aromatic Substitution: The Role of Electronically Excited States

Electrophilic aromatic substitutions (EAS), one of the most extensively studied organic reactions, can be considered under certain circumstances as a photochemical reaction without light. Thermochemical considerations show that in the gas phase, the reaction system (electrophile plus aromatic neutral) is often found initially in an electronically excited state, whereas the reaction products are formed on the ground state potential energy surface (PES). The crossing to the ground state is usually very rapid, so that the rate-determining steps take place on the ground state surface. It is shown that after the crossing (through a conical intersection (CI)), the system can be found on different parts of the ground state potential surface. In particular, the CI is connected without a barrier to all moieties assumed to be important in the reaction (pi complex, radical pair, and sigma complex). In some cases, due to a relatively low electron affinity of the electrophile and bond reorganization, the reaction starts on the ground state PES; a conical intersection exists in these cases, but is not accessed by the reactants. The topology of the reaction surface due to the avoided crossing is reminiscent of that in which an actual crossing takes place. The paper provides a comprehensive model for several EAS reactions. The CIs are located computationally, and an energy level diagram is proposed for some representative EAS reactions.

Multidimensional quantum-beat spectroscopy: Towards the complete temporal and spatial resolution of the nuclear dynamics in small molecules

We propose a multidimensional (MD) pump-probe method to image the coupled rovibrational (RV) nuclear dynamics in small molecules. We apply this imaging method to analyze the laser-induced coherent RV nuclear dynamics in ${\text{D}}_{2}^{+}$ in terms of MD quantum-beat (QB) spectra, without and including an external laser field, by solving the time-dependent Schr\"odinger equation in full dimensionality. These spectra resolve the internuclear distance $R$ and molecular orientation and reveal (1) the transition frequencies between stationary vibrational and rotational states, (2) their nodal structures, (3) RV couplings, including (4) their influence on the nuclear dynamics on field-free ground state and laser-dressed potential surfaces, and (5) offer an interpretation for an unexplained structure in recently measured QB spectra.

UV Photodissociation of Cyanoacetylene: A Combined Ion Imaging and Theoretical Investigation

The photodissociation of cyanoacetylene, one of the key minor constituents in Titan's atmosphere, was studied in a molecular beam under collisionless conditions using direct current slice ion imaging at 121.6, 193.3, and 243.2 nm. The experimental results were augmented by high-level theoretical calculations of stationary points on the ground-state and second excited singlet potential surfaces, and by statistical calculations of the dissociation rates and product branching on the ground-state surface. Results at 121.6 and 243.2 nm are nearly identical, suggesting that the 243.2 nm photodissociation is the result of a two-photon process. The translational energy distributions show only a modest fraction of the available energy in translation and are consistent with barrierless dissociation from the ground state. The results at 193.3 nm are quite distinct, showing up to half of the available energy in translation, implying dissociation with an exit barrier. The 193 nm result is ascribed to dissociation on the S(1) potential energy surface. The theoretical calculations show significant rates for H loss on the ground state at 193 nm and significant branching to CN + CCH at 157 nm and higher.

Density Functional Study of Intradimer Proton Transfers in Hydrated Adenine Dimer Ions, A2+(H2O)n (n = 0−2)

Structures of mono- and dihydrated adenine dimers and their cations were calculated using B3LYP density functional theory with the 6-31+G(d,p) basis set, in order to help understand photofragmentation experiments of hydrated adenine dimers from the energetics point of view. Several important pathways leading to the major fragmentation product, protonated adenine ion (AH(+)), thermodynamically at minimum costs were investigated at the ground-state electronic potential surface of hydrated adenine dimer cations. Our calculations suggest that the proton transfer from one adenine moiety to the other in hydrated dimer ions readily occurs with negligible barriers in normal hydration conditions. In asymmetrically hydrated ions, however, the proton transfer to more hydrated adenine moieties is kinetically hindered due to heightened transition-state barriers, while the other way is still barrierless. Such directional preference in proton transfer may be characterized as a unique dimer ion property, stemming from the difference in basicity of the two nitrogen atoms involved in the double hydrogen bond that would be equivalent without hydration. We also found that dimer cleavage requires about 4 times larger energy than evaporation of individual water molecules, so it is likely that most solvent molecules evaporate before the eventual dimer cleavage when available internal energy is limited.

DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes

Abstract The linkage isomers of the [M(NO)(CN)5]2− (M = Fe, Ru, Os), [Ru(NO)Cl5]2−, trans-[Ru(NO)(NH3)4(L)]q+ (L = NH3, H2O, nicotinamide, imidazole, pyridine, pyrazine, NO2 −, OH−, Cl−), and trans-[Ru(NO)L4(OH)]q (L = pyridine, NO2 −) ions are studied by density functional theory. DFT calculations show that the electronic ground-state potential surface of these nitrosyl complexes has the local minima corresponding to η 2-NO and η 1-O linkage isomers, of which the former is characterized by lower energy. The stationary points on the ground state potential energy surface along the GS → MS2 → MS1 path for the [M(NO)(CN)5]2− (M = Fe, Ru, Os) and [Ru(NO)Cl5]2− complexes were found. The calculations of infrared spectra of linkage isomers [Ru(NO)Cl5]2− and [Ru(NO)(CN)5]2− are carried out. The analysis of quantum chemical bond orders indicates a noticeable delocalization of π-electron density along the Ltrans—M—NO axis and a possibility of direct interactions between NO and equatorial ligands in the structures with the bent {MNO} group.

Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them

Abstract In this note, we reviewed theoretical investigations of the photo-induced metastable states and discussed possible photo-rearrangement paths in [M(CN)5NO]2− (M = Fe and Ru). Using calculated results of ab initio multi-reference single and double excitation configuration interaction calculations with Davidson type quadruple correction (MRSDCI + Q) and those of density fuctional theory (DFT), we showed that the two metastable states (MS1 and MS2) were local minima of the electronic ground state potential surface. The theoretical calculations supported the experimental observation of the structure of the three isomers (GS, MS1 and MS2), relative stability of MS1 and MS2. We discussed the character of the lower electronic excited states and excitation energies of the three isomers of both compounds. Based on these results and excited state adiabatic potential energy surfaces, possible mechanism of photo-rearrangement among GS, MS1, and MS2 were discussed with the aid of our results on [Mn(CN)5NO]3− of which no photo-rearrangement has been reported.

The geometry, vibrational frequencies, thermochemistry, quadrupole moments and electronic structure of C 2Na 2: Comparison with C 2Li 2, C 2H 2, C 2F 2 and C 2Cl 2

The electronic structure of Na 2C 2 is studied using ab initio electronic structure methods and is compared to the companion molecule Li 2C 2. Both the linear D ∞ h and planar structures are minima on the ground state potential surface with the planar D 2 h conformation being the lowest energy form, similar to Li 2C 2. At the CCSD(t) level the planar form is more stable that the linear by 11.2 kcal/mol as compared with 7.34 kcal/mol for Li 2C 2. Both molecules are significantly ionic. The vibrational frequencies, atomization energy at 0 K, D 0, and the standard enthalpy of formation, Δ H 0 f are calculated and compared to those of Li 2C 2 as well as HCCH, FCCF and ClCCCl. We find D 0 and Λ H 0 f to be 331.1 and 84.92 kcal/mol for Li 2C 2 and 298.3 and 93.25 kcal/mol for Na 2C 2. We calibrate these by calculating the same quantities for HCCH, FCCF and ClCCCl.

Quantum control of a chiral molecular motor driven by femtosecond laser pulses: Mechanisms of regular and reverse rotations

Rotational mechanisms of a chiral molecular motor driven by femtosecond laser pulses were investigated on the basis of results of a quantum control simulation. A chiral molecule, ( R)-2-methyl-cyclopenta-2,4-dienecarboaldehyde, was treated as a molecular motor within a one-dimensional model. It was assumed that the motor is fixed on a surface and driven in the low temperature limit. Electric fields of femtosecond laser pulses driving both regular rotation of the molecular motor with a plus angular momentum and reverse rotation with a minus one were designed by using a global control method. The mechanism of the regular rotation is similar to that obtained by a conventional pump–dump pulse method: the direction of rotation is the same as that of the initial wave packet propagation on the potential surface of the first singlet ( n π ∗ ) excited state S 1 . A new control mechanism has been proposed for the reverse rotation that cannot be driven by a simple pump–dump pulse method. In this mechanism, a coherent Stokes pulse creates a wave packet localized on the ground state potential surface in the right hand side. The wave packet has a negative angular momentum to drive reverse rotation at an early time.