Fluctuations in electronegativity and global hardness induced by molecular vibrations

A pair of novel molecular indices has been proved to contain important information on the coupling between atomic displacement and electronic properties based on the electron density function within the Density Functional Theory: the nuclear reactivity (Φ) and nuclear stiffness (G). Appropriate calculation procedure has been developed and their role in describing anharmonicity of diatomic molecules has been demonstrated. This present work provides analysis of this effect for small molecules, unveiling the role of symmetry of molecular vibrational modes in modifying the affinity of a molecule to intermolecular electron transfer. The indices have been found to be a crucial factor determining thermal fluctuations in the molecular energy derivatives: electronegativity (χ) and hardness (η). The fluctuations of hardness play a specific role, as they bring a molecule uniquely to a critical region (η0), when molecule becomes unstable to an electron exchange process, due to its excitation in a selected destructive vibrational mode.     

Ultrafast S1 to S0 internal conversion dynamics for dimethylnitramine through a conical intersection

Electronically nonadiabatic processes such as ultrafast internal conversion (IC) from an upper electronic state (S(1)) to the ground electronic state (S(0)) though a conical intersection (CI), can play an essential role in the initial steps of the decomposition of energetic materials. Such nonradiative processes following electronic excitation can quench emission and store the excitation energy in the vibrational degrees of freedom of the ground electronic state. This excess vibrational energy in the ground electronic state can dissociate most of the chemical bonds of the molecule and can generate stable, small molecule products. The present study determines ultrafast IC dynamics of a model nitramine energetic material, dimethylnitramine (DMNA). Femtosecond (fs) pump-probe spectroscopy, for which a pump pulse at 271 nm and a probe pulse at 405.6 nm are used, is employed to elucidate the IC dynamics of this molecule from its S(1) excited state. A very short lifetime of the S(1) excited state (～50 ± 16 fs) is determined for DMNA. Complete active space self-consistent field (CASSCF) calculations show that an (S(1)/S(0))(CI) CI is responsible for this ultrafast decay from S(1) to S(0). This decay occurs through a reaction coordinate involving an out-of-plane bending mode of the DMNA NO(2) moiety. The 271 nm excitation of DMNA is not sufficient to dissociate the molecule on the S(1) potential energy surface (PES) through an adiabatic NO(2) elimination pathway.     

Competitive ionization processes of anthracene excited with a femtosecond pulse in the multi-photon ionization regime

To clarify the ionization mechanism of large molecules under multi-photon ionization conditions, photo-electron spectroscopic studies on anthracene have been performed with electron imaging technique. Electron kinetic energy distributions below a few eV reveal that three kinds of ionization channels coexist, viz., vertical ionization, ionization from Rydberg states, and thermionic hot electron emission. Their relative yield is determined by the characteristic of the laser pulse. The duration in particular influences the ratio between the first two processes, while for higher intensities the last process dominates. Our results provide strong evidence that internal conversion plays an important role for the ionization of the molecule.     

Spectroscopic and theoretical studies on nickel(II) complex of maleonitriledithiolate and 2,2'-bipyridine

The complete IR spectra of the title complex Ni(mnt)(bpy) (mnt=maleonitriledithiolate, bpy=2,2'-bipyridine) and a new method to analyze vibrational spectra for such a complicated metal complex are reported in this paper. The molecular geometry, binding, electronic structure and spectroscopic property of it have been studied in detail by theoretical calculations. The geometry optimization from PM3 calculations give that this molecule is of a planar structure with the symmetry point group C(2v) and its ground state is the spin triplet state. The vibrational and electronic spectra were calculated by PM3 and ZINDO/S methods, respectively. The scientific method of analyzing vibrational spectra is established herein by giving main fixed points and pivotal vibrational units. Besides the regular symbols, the new defined symbols eta and M play an important role in describing the vibration modes accurately and vividly.     

Femtosecond excited state studies of the two-center three-electron bond driven twisted internal charge transfer dynamics in 1,8-bis(dimethylamino)naphthalene

Femtosecond fluorescence upconversion and transient absorption experiments have been performed to monitor the photoinduced electronic, geometry, and solvent relaxation dynamics of 1,8-bis(dimethylamino)naphthalene dissolved in methylcyclohexane or n-hexane, n-dodecane, dichloromethane, and acetonitrile. The data have been analyzed by using a sequential global analysis method that gives rise to species associated difference spectra. The spectral features in these spectra and their dynamic behavior enable us to associate them with specific processes occurring in the molecule. The experiments show that the internal charge-transfer lpi* state is populated after internal conversion from the 1La state. In the lpi state the molecule is concluded to be subject to a large-amplitude motion, thereby confirming our previous predictions that internal charge transfer in this state is accompanied by the formation of a two-center three-electron bond between the two nitrogen atoms. Solvent relaxation and vibrational cooling in the lpi* state cannot be separated in polar solvents, but in apolar solvents a distinct vibrational cooling process in the lpi* state is discerned. The spectral and dynamic characteristics of the final species created in the experiments are shown to correspond well with what has been determined before for the relaxed emissive lpi state.     

Dynamics of highly excited nitroaromatics

Although the photodissociation of nitroaromatics in low excitation electronic states has been extensively studied in recent decades, little is known about the highly excited electronic states. The fragmentation dynamics of three nitroaromatics, nitrobenzene, o-nitrotoluene, and m-nitrotoluene, in highly excited states, populated by the absorption of two photons at 271 nm, are studied with time-of-flight mass spectrometry. The temporal evolutions of the highly excited states are monitored by one-photon ionization at 408 nm. The transients of parent and fragment ions exhibit two ultrafast deactivation processes. The first process is ultrafast internal conversion from the initial excitation to Rydberg states in tens of femtoseconds. The second one is conversion from the Rydberg states to the vibrational manifold in the ground electronic states within hundreds of femtoseconds. The internal conversion process is accelerated by methyl substitution. In o-nitrotoluene, the two processes become much faster due to the hydrogen transfer from the CH(3) to the NO(2) group (ortho effect).     

A beta-naphthaleneimide-modified terthiophene exhibiting charge transfer and polarization through the short molecular axis. Joint spectroscopic and theoretical study

We present a new terthiophene derivative substituted at the thienyl beta positions with a naphthalenediimide functionalization. The UV-vis absorption and emission spectroscopic properties as well as the electrochemical properties have been discussed to describe its electronic structure. The vibrational Raman data are used to inspect the molecular architecture. All of the experimental data are supported by quantum chemical calculations with different approaches. A close comparison with other terthiophenes available in the literature is conducted, always stressing the effect of the relative orientation of the donor and acceptor groups either with long-axis or short-axis polarizations. The electronic structure of the molecule has been understood in terms of the HOMO-LUMO absolute energy values. A considerable reduction of the band gap from the constituting units to the studied molecule is detected, although electronic interaction is not optimal for this configuration. Fluorescence quenching is interpreted by the possibility of intersystem crossing and internal conversion. Finally, Raman spectroscopy gives additional information of the distribution of conjugation along the molecular domain, of subtle conformational effects, and of the intermolecular interaction by means of temperature-dependent Raman data. This study provides guidelines for controlling the electronic structure and for exploring new strategies pursuing improved dyes.     

Early time hydrogen-bonding dynamics of photoexcited coumarin 102 in hydrogen-donating solvents: theoretical study

To study the early time hydrogen-bonding dynamics of chromophore in hydrogen-donating solvents upon photoexcitation, the infrared spectra of the hydrogen-bonded solute-solvent complexes in electronically excited states have been calculated using the time-dependent density functional theory (TDDFT) method. The hydrogen-bonding dynamics in electronically excited states can be widely monitored by the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds. In this study, we have demonstrated that the intermolecular hydrogen bonds between coumarin 102 (C102) and hydrogen-donating solvents are strengthened in the early time of photoexcitation to the electronically excited state by theoretically monitoring the stretching modes of C=O and H-O groups. This is significantly contrasted with the ultrafast hydrogen bond cleavage taking place within a 200-fs time scale upon electronic excitation, proposed in many femtosecond time-resolved vibrational spectroscopy experiments. The transient hydrogen bond strengthening behaviors in excited states of chromophores in hydrogen-donating solvents, which we have demonstrated here for the first time, may take place widely in many other systems in solution and are very important to explain the fluorescence-quenching phenomena associated with some radiationless deactivation processes, for example, the ultrafast solute-solvent intermolecular electron transfer and the internal conversion process from the fluorescent state to the ground state.     

Vibrational properties of the compressed and the relaxed 1,4,5,8-naphthalene-tetracarboxylic dianhydride monolayer on Ag(111)

Layers of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) grown on Ag(111) at about 80 K have been investigated using Fourier transform infrared spectroscopy, spot profile analysis low-energy electron diffraction, and temperature programmed desorption. Specifically, the compressed and the relaxed monolayer, as well as the transformation between the two ordered phases have been analyzed in detail. It is found that the two monolayer phases display distinctly different vibrational spectra and can thus be discriminated with high accuracy and sensitivity. For the NTCDA/Ag(111) monolayer strong in-plane vibrational modes point at a marked dynamic charge transfer between molecule and metal substrate and provide clear evidence for an efficient electronic coupling to the Ag(111) surface in conjunction with a partially filled electronic level at the Fermi energy. The bilayer, on the other hand, is largely electronically decoupled from the substrate and, according to the vanishing infrared-active in-plane vibrational modes, is oriented parallel to the surface. On the basis of spectroscopic data the metastable nature of the bilayer phase is identified as such, leading to an improved understanding of processes encountered in the course of layer preparation and resolving inconsistencies reported in the literature.     

Relating normal vibrational modes to local vibrational modes with the help of an adiabatic connection scheme

Information on the electronic structure of a molecule and its chemical bonds is encoded in the molecular normal vibrational modes. However, normal vibrational modes result from a coupling of local vibrational modes, which means that only the latter can provide detailed insight into bonding and other structural features. In this work, it is proven that the adiabatic internal coordinate vibrational modes of Konkoli and Cremer [Int. J. Quantum Chem. 67, 29 (1998)] represent a unique set of local modes that is directly related to the normal vibrational modes. The missing link between these two sets of modes are the compliance constants of Decius, which turn out to be the reciprocals of the local mode force constants of Konkoli and Cremer. Using the compliance constants matrix, the local mode frequencies of any molecule can be converted into its normal mode frequencies with the help of an adiabatic connection scheme that defines the coupling of the local modes in terms of coupling frequencies and reveals how avoided crossings between the local modes lead to changes in the character of the normal modes.     

Dynamics of clusters initiated by photon and surface impact

Clusters of atoms/molecules show dynamics characteristic of the method of excitation. Two contrasted processes are discussed: (1) electronic excitation via single-photon absorption and (2) impulsive excitation of nuclear motions by surface impact. Process 1 is exemplified by photodissociation dynamics of size-selected metal cluster ions. The electronic energy is converted most likely to vibrational energy of internal modes; dissociation follows via statistical mechanism to produce energetically favored fragments. Exceptionally, a silver cluster ion, Ag4(+), is shown to undergo nonstatistical dissociation along the potential-energy surface of the excited state. Energy partitioning to translational and vibrational modes of fragments is analyzed as well as bond dissociation energies. Furthermore, the spectrum of the photodissociation yield provides electronic and geometrical structures of a cluster with the aid of ab initio calculations; manganese, Mn(N)(+), and chromium, Cr(N)(+), cluster ions are discussed, where the importance of magnetic interactions is manifested. On the other hand, momentum transfer upon surface impact plays a role in process 2. An impulsive mechanical force triggers extraordinary chemical processes distinct from those initiated by atomic collision as well as photoexcitation. Experiments on aluminum, Al(N)(-), silicon, SiN(-), and solvated, I(2)(-)(CO2)(N), cluster anions provide evidence for reactions proceeding under extremely high temperatures, such as pickup of surface atoms, annealing of products, and mechanical splitting of chemical bonds. In addition, a model experiment to visualize and time-resolve the cluster impact process is performed by using a micrometer-sized liquid droplet. Multiphoton absorption initiates superheating of the droplet surface followed by a shock wave and disintegration into a number of small fragments (shattering). These studies further reveal how the nature of chemical bonds influences the dynamics of clusters.     

Note on the role of vibrational modes in molecular electronic transitions

A simple application of a readily available quantum chemistry program (AMPAC) permits an illuminating presentation of the role of vibrational modes in electronic transitions. A direct comparison of modal surfaces for different electronic states of the same molecule can be made by using a perspective plot of the Duschinsky matrix for the transition with mode indices or eigenvalue sequence, as the planar axes. The sum of squares of the off-diagonal elements of the Duschinsky matrix can be used to give a measure of the difference between vibrational modes of the initial and final states. Calculations indicate that, in biacetyl, the triplet state is closer vibrationally to the anion ground state than either the singlet or the neutral ground state, while in glyoxal the ground state neutral has greater vibrational similarity to the anion ground state. The measure also indicates little change in vibrational modes upon intersystem crossing in formaldehyde.     

Quantum simulation of solution phase intramolecular electron transfer rates in betaine-30

Mixed quantum-classical atomistic simulations have been carried out to investigate the mechanistic details of excited state intramolecular electron transfer in a betaine-30 molecule in acetonitrile. The key electronic degrees of freedom of the solute molecule are treated quantum mechanically using the semiempirical Pariser-Parr-Pople Hamiltonian, including the solvent influence on electronic structure. The intramolecular vibrational modes are also treated explicitly at a quantum level, with the remaining elements treated classically using empirical potentials. The electron-transfer rate, corresponding to S1 --> S0 relaxation, is evaluated via time-dependent perturbation theory with the explicit inclusion of the dynamics of solvation and intramolecular conformation. The calculations reveal that, while solvation dynamics is critical to the rate, the intramolecular torsional dynamics also plays an important role. The importance of the use of multiple high-frequency quantum modes is also discussed.     

Radiationless transitions and population inversions: Two examples of internal conversion

A theory of internal conversion between two displaced harmonic modes is shown to imply that the coupling strength increases with the initial excess vibrational energy. The same molecule (or collision pair) can exhibit both weak and strong coupling (i.e. both enhancement and retardation of the conversion probability by the initial vibrational energy).     

Excited-state dynamics of trans,trans-1,3,5,7-octatetraene: estimation of decay rate constants of 1(1)B(u) ⇝ 2(1)A(g) and 2(1)A(g) ⇝ 1(1)A(g) internal conversions

The general expressions we previously derived for calculating internal conversion rate constants between two adiabatic displaced-distorted-rotated potential energy surfaces, by including all vibratinal modes, are applied to estimate the decay rate constants of 1(1)B(u) ? 2(1)A(g) and 2(1)A(g) ? 1(1)A(g) internal conversions in trans,trans-1,3,5,7-octatetraene molecule. The minimal models with respect to the number and types of vibrational modes are determined for these processes. Our calculations show that in the low temperature limit the 1(1)B(u) ? 2(1)A(g) internal conversion takes place on a 232-290 fs time scale in the condensed phase and 2 ps in the gas phase, whereas 2(1)A(g) ? 1(1)A(g) internal conversion takes place on a 2 μs time scale under the isolated conditions.     

On the possibility of the role of phonon relaxation processes in shock induced chemical reactions in organic solids

The possibility that the first step in shock breaking of intra molecular bonds of molecules in organic solids involves a transfer of lattice phonons to internal molecular vibrational modes of the molecule is examined. Rates of transfer to specific vibrations of RDX are calculated as a function of shock pressure. The results suggest the possibility of the process.     

RDX分子内振动能量重分配的动力学研究

基于从头算分子动力学(Born-oppenheimer molecular dynamics, BOMD)模拟, 构建了环硝胺六氢-1,3,5-三硝基-1,3,5-三嗪(RDX)单分子不同振动模式之间的耦合矩阵, 并计算了在不同加载能量下从低频振动模式到高频振动模式的最优能量传输路径. 结果表明, RDX单分子中—NNO₂基团更有利于能量局域化, 振动模式v₃和v₄在从低频振动模式到高频振动模式的能量传输过程中扮演着重要角色. 通过对v₃和v₄两个振动模式的进一步分析发现, 加载能量的不同会导致RDX单分子能量传输路径的不同. 当加载能量较低时, RDX单分子倾向于从低频振动模式到中频振动模式再到高频振动模式的能量传输路径; 当加载能量较高时, 能量更倾向于从低频振动模式直接传输到高频振动模式上. 揭示了RDX分子内振动耦合能量转移的微观机制, 为进一步探索RDX将“机械能”转化为“化学能”的微观过程提供了理论基础.     

Molecular dynamics integration and molecular vibrational theory. I. New symplectic integrators

New symplectic integrators have been developed by combining molecular dynamics integration with the standard theory of molecular vibrations to solve the Hamiltonian equations of motion. The presented integrators analytically resolve the internal high-frequency molecular vibrations by introducing a translating and rotating internal coordinate system of a molecule and calculating normal modes of an isolated molecule only. The translation and rotation of a molecule are treated as vibrational motions with the vibrational frequency zero. All types of motion are thus described in terms of the normal coordinates. The method's time reversibility requirement was used to determine the equations of motion for internal coordinate system of a molecule. The calculation of long-range forces is performed numerically within the generalized second-order leap-frog scheme, in the same way as in standard second-order symplectic methods. The new methods for integrating classical equations of motion using normal mode analysis allow us to use a long integration step and are applicable to any system of molecules with one equilibrium configuration.     

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.

Channelling vibrational excitation energy to achieve ground-state charge-transfer (CT)-assisted isomerization in a donor-bridge-acceptor molecule in solution.