Photochemistry. A modern theoretical perspective

This book offers an introduction to photochemistry for students with a minimal background in physical chemistry and molecular quantum mechanics. The focus is from a theoretical perspective and highlights excited state dynamics. The authors, experienced lecturers, describe the main concepts in photochemical and photophysical processes that are used as a basis to interpret classical steady-state experimental results (essentially product branching ratios and quantum yields) and the most advanced time-resolved techniques. A significant portion of the content is devoted to the computational techniques present in quantum chemistry and molecular dynamics. With its short summaries, questions and exercises, this book is aimed at graduate students, while its theoretical focus differentiates it from most introductory textbooks on photochemistry

An overview of nonadiabatic dynamics simulations methods, with focus on the direct approach versus the fitting of potential energy surfaces

We review state-of-the-art nonadiabatic molecular dynamics methods, with focus on the comparison of two general strategies: the "direct" one, in which the potential energy surfaces (PES) and the couplings between electronic states are computed during the integration of the dynamics equations; and the "PES-fitting" one, whereby the PES and couplings are preliminarily computed and represented as functions of the nuclear coordinates. Both quantum wavepacket dynamics (QWD) and classical trajectory approaches are considered, but we concentrate on methods for which the direct strategy is viable: among the QWD ones, we focus on those based on traveling basis functions. We present several topics in which recent progress has been made: quantum decoherence corrections in trajectory methods, the use of quasi-diabatic representations, the sampling of initial conditions and the inclusion of field-molecule interactions and of spin-orbit couplings in the dynamics. Concerning the electronic structure calculations, we discuss the use of ab initio, density functional and semiempirical methods, and their combination with molecular mechanics (QM/MM approaches). Within the semiempirical framework, we provide a concise but updated description of our own method, based on configuration interaction with floating occupation molecular orbitals. We discuss the ability of different approaches to provide observables directly comparable with experimental results and to simulate a variety of photochemical and photophysical processes. In the concluding remarks, we stress how the border between direct and PES-fitting methods is not so sharp, and we briefly discuss recent trends that go beyond this traditional distinction

Temporal and spatial constructs in service firms' internationalization patterns: The determinants of the accelerated growth of Emerging MNEs

AbstractThe recent years have witnessed an unprecedented surge of Emerging Multinational Enterprises (EMNEs), i.e. firms from the emerging economies that have started internationalization very late and have expanded abroad in a rather accelerated fashion.In particular, pace and international diversification emerge as distinctive features of service EMNEs' successful internationalization patterns, inducing scholars to question the applicability of traditional internationalization theories to EMNEs. The Linkage–Leverage–Learning (LLL) Model and the springboard perspective identified some of the critical EMNEs uniqueness and investigated potential antecedents of their abnormal patterns. Nevertheless, previous contributions neglected to provide a solid empirical base for measuring spatio-temporal dimensions of EMNEs' internationalization.This paper aims to empirically investigate the dimensions affecting the pace at which EMNEs enlarge their geographic scope, by performing OLS regression analysis.The main outcomes demonstrate the crucial role of cumulative benefits from inward internationalization and inter-regional diversification strategies in boosting EMNEs' overseas expansion, in opposition to traditional MNEs (TMNEs). The results corroborate some assumptions of emerging theories on EMNEs, and provide insight for extending traditional MNEs theories by rethinking concepts, relations and causalities

The photo-orientation of azobenzene in viscous solutions, simulated by a stochastic model

We report a computational study of the photo-orientation kinetics in a viscous solution of azobenzene in ethylene glycol, under irradiation with linearly polarized light. The development of anisotropy and its interplay with photoisomerization are simulated by a stochastic model. A distinctive feature of the model is that it takes into account the photo-orientation angular distributions, specific for each isomer, obtained by nonadiabatic dynamics simulations at the molecular level. We find that the anisotropy, as measured by optical absorption dichroism, does not necessarily increase monotonously with time. As expected, the photo-orientation turns out to be strongly coupled with photoisomerization, but the latter is not a mandatory ingredient of this phenomenon: we predict that any chromophore undergoing large amplitude geometry relaxation during its excited state dynamics can develop anisotropy under suitable conditions

Nonadiabatic dynamics simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene crystals

We present simulations of the singlet fission dynamics in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF), a thienoquinoid compound recently investigated experimentally by Kawata et al. The simulation model consisted of two ThBF molecules embedded in their crystal environment. The aim was to understand the singlet fission mechanism, and to predict the excited state lifetimes and the singlet fission quantum yield, hitherto unknown. The simulations were performed by the trajectory surface hopping approach with on-the-fly calculations of the electronic wave functions and energies by the semiempirical FOMO-CI method. We found that the initially photogenerated excitonic bright state decays to the lower dark state with a biexponential behaviour, essentially due to transitions to other close lying states. The dark state in turn decays with a lifetime of about 1 ps to the double triplet 1TT state, which is long-lived, as ascertained by performing a simulation with inclusion of the spin-orbit coupling. The singlet fission quantum yield is predicted to be close to the theoretical maximum of 200%. In view of using this thienoquinoid compound in photovoltaic devices, a major drawback is the low energy of the T1 state at its equilibrium geometry

Dynamics of acetone photodissociation: a surface hopping study

We present on the fly surface hopping simulations of the dynamics of photoexcited acetone in the n->pi* band, taking into account both the spin-orbit and the dynamic couplings and allowing for the C-C bond dissociation. The S0, S1, T1 and T2 states were considered and the propagation time was 50 ps. According to the simulation results, after excitation to S1 both Internal Conversion (IC) to S0 and InterSystem Crossing (ISC) to T1 or T2 take place at comparable rates; T2 plays an important role and the simultaneous treatment of the spin-orbit and dynamic couplings is shown to be mandatory to describe the photodynamics. We propose a mechanism that explains the observed fast and slow decay rates of the S1 state of acetone

Surface hopping investigation of benzophenone excited state dynamics

We present a simulation of the photodynamics of benzophenone for the first 20 ps after n -> pi* excitation, performed by trajectory surface hopping calculations with on-the-fly semiempirical determination of potential energy surfaces and electronic wavefunctions. Both the dynamic and spin-orbit couplings are taken into account, and time-resolved fluorescence emission is also simulated. The computed decay time of the S-1 state is in agreement with experimental observations. The direct S-1 -> T-1 intersystem crossing (ISC) accounts for about 2/3 of the S-1 decay rate. The remaining 1/3 goes through T-2 or higher triplets. The nonadiabatic transitions within the triplet manifold are much faster than ISC and keep the population of T-1 at about 3/4 of the total triplet population, and that of the other states (mainly T-2) at 1/4. Two internal coordinates are vibrationally active immediately after n -> pi* excitation: one is the C-O stretching and the other one is a combination of the conrotatory torsion of phenyl rings and of bending involving the carbonyl C atom. The period of the torsion-bending mode coincides with oscillations in the time-resolved photoelectron spectra of Spighi et al. and substantially confirms their assignment

Metastatic tumors to the stomach: clinical and endoscopic features.

AIM: To evaluate the clinical and endoscopic patterns in a large series of patients with metastatic tumors in the stomach. METHODS: A total of 64 patients with gastric metastases from solid malignant tumors were retrospectively examined between 1990 and 2005. The clinicopathological findings were reviewed along with tumor characteristics such as endoscopic pattern, location, size and origin of the primary sites. RESULTS: Common indications for endoscopy were anemia, bleeding and epigastric pain. Metastases presented as solitary (62.5%) or multiple (37.5%) tumors were mainly located in the middle or upper third of stomach. The main primary metastatic tumors were from breast and lung cancer and malignant melanoma. CONCLUSION: As the prognosis of cancer patients has been improving gradually, gastrointestinal (GI) metastases will be encountered more often. Endoscopic examinations should be conducted carefully in patients with malignancies, and endoscopic biopsies and information on the patient's clinical history are useful for correct diagnosis of gastric metastases

Capsule impaction presenting as acute small bowel perforation: a case series

INTRODUCTION: Perforation caused by capsule endoscopy impaction is extremely rare and, at present, only five cases of perforation from capsule endoscopy impaction are reported in the literature. CASE PRESENTATION: We report here two cases of patients with undiagnosed small bowel stenosis presenting with acute perforation after capsule endoscopy. Strictures in the small bowel were likely the inciting mechanism leading to acute small bowel obstruction and subsequent distension and perforation above the capsule in the area of maximal serosal tension. Case 1 was a 55-year-old Italian woman who underwent capsule endoscopy because of recurrent postprandial cramping pain and iron deficiency anemia, in the setting of negative imaging studies including an abdominal ultrasound, upper endoscopy, colonoscopy and small bowel follow-through radiograph. She developed a symptomatic bowel obstruction approximately 36 hours after ingestion of the capsule. Emergent surgery was performed to remove the capsule, which was impacted at a stenosis due to a previously undiagnosed ileal adenocarcinoma, leading to perforation. Case 2 was a 60-year-old Italian man with recurrent episodes of abdominal pain and diarrhea who underwent capsule endoscopy after conventional modalities, including comprehensive blood and stool studies, computed tomography, an abdominal ultrasound, upper endoscopy, colonoscopy, barium enema and small bowel follow-through, were not diagnostic. Our patient developed abdominal distension, acute periumbilical pain, fever and leukocytosis 20 hours after capsule ingestion. Emergent surgery was performed to remove the capsule, which was impacted at a previously undiagnosed ileal Crohn’s stricture, leading to perforation. CONCLUSIONS: The present report shows that, although the risk of acute complication is very low, the patient should be informed of the risks involved in capsule endoscopy, including the need for emergency surgical exploration

Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions

We implemented a method for the treatment of field induced transitions in trajectory surface hopping simulations, in the framework of the local diabatization scheme, especially suited for on-the-fly dynamics. The method is applied to a simple one-dimensional model with an avoided crossing and compared with quantum wavepacket dynamics. The results show the importance of introducing a proper decoherence correction to surface hopping, in order to obtain meaningful results. Also the energy conservation policy of standard surface hopping must be revised: in fact, the quantum wavepacket energetics is well reproduced if energy absorption/emission is allowed for in the hops determined by radiation-molecule coupling. To our knowledge, this is the first time the issues of decoherence and energy conservation have been analyzed in depth to devise a mixed quantum-classical method for dynamics with molecule-field interactions