Unprecedented C-F bond cleavage in perfluoronaphthalene during cobaltocene reduction.

The C-F bond activation of perfluoronaphthalene by 5-SIDipp led to the formation of dicationic salts with two fluorides (3·2HF2 ) or heptafluorodiborate (3·2B2F7) as counter-anions. The anion exchange reaction of 3·2B2F7 with NBuPF afforded a highly luminescent 3·2PF6. The addition of cobaltocene in the reaction mixture of 5-SIDipp and perfluoronaphthalene led to a distinct Co(I) species.

Relaxation of the 2a1 ionized water dimer: An interplay of intermolecular Coulombic decay (ICD) and proton transfer processes.

This article investigates the relaxation dynamics of the ionized 2a1 state of a water molecule within a water dimer. The study was motivated by findings from two previous pieces of research that focused on the relaxation behaviors of the inner-valence ionized water dimer. The present study discloses an observation indicating that water dimers display specific fragmentation patterns following inner-valence ionization, depending on the position of the vacancy.

Full Dynamical and Ab Initio Investigation of the Electron Transfer-Mediated Decay Mechanism of He in the Presence of Heavier Alkali Dimers.

We have studied the electron transfer-mediated decay (ETMD) process for the 1s ionized state of the He atom in the presence of a heavier alkali homonuclear dimer (Na, K, and Rb) as well as heteronuclear dimer (LiNa, NaK, and KRb). In our computation, we have considered all the alkali dimers being in the singlet electronic ground state. The electron transfer from the alkali dimer to He (1s) leads to the emission of another electron from the alkali dimer into the continuum.

Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters.

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)n and Mg2+-(H2O)n (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules.

Enhancing Diradical Character of Chichibabin's Hydrocarbon through Fluoride Substitution.

In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin's hydrocarbon with an octafluorobiphenylene spacer (3) has been reported. The addition of two equivalents of 5-SIDipp with decafluorobiphenyl in presence of BF gives the double C-F bond activated imidazolium salt with two tetrafluoroborate anions, 2. Further reduction of 2 gives the fluorine substituted 5-SIDipp based Chichibabin's hydrocarbon, 3.

Decay Processes in Cationic Alkali Metals in Microsolvated Clusters: A Complex Absorbing Potential Based Equation-of-Motion Coupled Cluster Investigation.

We have employed the highly accurate complex absorbing potential based ionization potential equation-of-motion coupled cluster singles and doubles (CAP-IP-EOM-CCSD) method to study the various intermolecular decay processes in ionized metals (Li, Na, K) microsolvated by water molecules. For the Li atom, the electron is ionized from the 1s subshell. However, for Na and K atoms, the electron is ionized from 2s and both 2s and 2p subshells, respectively.

Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters. We considered two HeLi clusters - with Li being either in the singlet electronic ground state or in the triplet first excited state - in which ETMD takes place after ionization of He. The electron transfer from Li to He leads to the emission of another electron from Li into the continuum.

Attosecond spectroscopy reveals alignment dependent core-hole dynamics in the ICl molecule.

The removal of electrons located in the core shells of molecules creates transient states that live between a few femtoseconds to attoseconds. Owing to these short lifetimes, time-resolved studies of these states are challenging and complex molecular dynamics driven solely by electronic correlation are difficult to observe. Here, we obtain few-femtosecond core-excited state lifetimes of iodine monochloride by using attosecond transient absorption on iodine 4d6p transitions around 55 eV.

Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CHI.

The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser.

Electron transfer mediated decay in HeLi cluster: Potential energy surfaces and decay widths.

Electron transfer mediated decay (ETMD) is a process responsible for double ionization of dopants in He droplets. It is initiated by producing He in the droplet, which is neutralized by ETMD, and has been shown to strongly enhance the dopant's double ionization cross section. The efficiency of ETMD, the spectra of emitted secondary electrons, and the character of the ionic products depend on the nuclear dynamics during the decay.

Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments.

The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H products of the formaldehyde dissociation.

Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method.

Auger decay is an efficient ultrafast relaxation process of core-shell or inner-shell excited atom or molecule. Generally, it occurs in femto-second or even atto-second time domain. Direct measurement of lifetimes of Auger process of single ionized and double ionized inner-shell state of an atom or molecule is an extremely difficult task.

Geometry-dependent lifetime of Interatomic coulombic decay using equation-of-motion coupled cluster method.

Electronically excited atom or molecule in an environment can relax via transferring its excess energy to the neighboring atoms or molecules. The process is called Interatomic or Intermolecular coulombic decay (ICD). The ICD is a fast decay process in environment.

Complex absorbing potential based equation-of-motion coupled cluster method for the potential energy curve of CO₂⁻ anion.

The equation-of-motion coupled cluster method employing the complex absorbing potential has been used to investigate the low energy electron scattering by CO2. We have studied the potential energy curve for the (2)Π(u) resonance states of CO2(-) upon bending as well as symmetric and asymmetric stretching of the molecule. Specifically, we have stretched the C-O bond length from 1.

CAP/EOM-CCSD method for the study of potential curves of resonant states.

The equation-of-motion coupled-cluster (EOM-CC) method along with the complex absorbing potential (CAP) is used for the study of resonance in e(-)-N2 and e(-)-CO. Resonance position and width are studied as a function of bond length. We report the potential curves (PC) of the resonance states.

Study of interatomic Coulombic decay of Ne(H2O)n (n = 1,3) clusters using equation-of-motion coupled-cluster method.

Interatomic Coulombic decay (ICD) is an efficient and ultrafast radiationless decay mechanism which can be initiated by removal of an electron from the inner-valence shell of an atom or molecule. Generally, the ICD mechanism is prevailed in weakly bound clusters. A very promising approach, known as CAP/EOM-CC, consists of the combination of complex absorbing potential (CAP) with the equation-of-motion coupled-cluster (EOM-CC) method, is applied for the first time to study the nature of the ICD mechanism.

Equation-of-motion coupled-cluster method for the study of shape resonance.

The equation-of-motion coupled-cluster method (EOM-CC) is applied for the first time to calculate the energy and width of a shape resonance in an electron-molecule scattering. The procedure is based on inclusion of complex absorbing potential with EOM-CC theory. We have applied this method to investigate the shape resonance in e(-)N(2), e(-)CO, and e(-)C(2)H(2).