Search results for " intersections"

Computational determination of the dominant triplet population mechanism in photoexcited benzophenone

2014

In benzophenone, intersystem crossing occurs efficiently between the S-1(n pi(star)) state and the T-1 state of dominant n pi(star) character, leading to excited triplet states after photoexcitation. The transition mechanism between S-1(n pi(star)) and T-1 is still a matter of debate, despite several experimental studies. Quantum mechanical calculations have been performed in order to assess the relative efficiencies of previously proposed mechanisms, in particular, the direct S-1 -> T-1 and indirect S-1 -> T-2(pi pi(star)) -> T-1 ones. Multiconfigurational wave function based methods are used to discuss the nature of the relevant states and also to determine minimum energy paths a…

Modelling Photoionisation in Isocytosine: Potential Formation of Longer‐Lived Excited State Cations in its Keto Form

2021

Abstract Studying the effects of UV and VUV radiation on non‐canonical DNA/RNA nucleobases allows us to compare how they release excess energy following absorption with respect to their canonical counterparts. This has attracted much research attention in recent years because of its likely influence on the origin of our genetic lexicon in prebiotic times. Here we present a CASSCF and XMS‐CASPT2 theoretical study of the photoionisation of non‐canonical pyrimidine nucleobase isocytosine in both its keto and enol tautomeric forms. We analyse their lowest energy cationic excited states including 2π+ , 2nO+ and 2nN+ and compare these to the corresponding electronic states in cytosine. Investigat…

Ultrafast decay of the excited singlet states of thioxanthone by internal conversion and intersystem crossing.

2010

The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high-level ab initio CASPT2 calculations of the singlet- and triplet-state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin-orbit coupling terms. The initially populated singlet pi pi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate n pi* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversio…

Reducing Air Pollutants through Road Innovative Intersections

2013

Road pollutant emissions are correlated mainly to infrastructural capacity and to traffic intensity and typology. With the aim to improve road intersections performances in the last years was designed many new geometric layouts, like turbo roundabouts and flower roundabouts. The main objective of this paper is carried out a comparative analysis between conventional and innovative roundabouts in terms of CO, CO2, NO and PM2,5 vehicular emissions, evaluated by means of COPERT Software which is developed as a European tool for the calculation of emissions from the road transport sector.

Accounting for dispersion and correlation in estimating Safety Performance Functions. An overview starting from a case study

2013

In statistical analysis of crash count data, as well as in estimating Safety Performance Functions (SPFs), the failure of Poisson equidispersion hypothesis and the temporal correlation in annual crash counts must be considered to improve the reliability of estimation of the parameters. After a short discussion on the statistical tools accounting for dispersion and correlation, the paper presents the methodological path followed in estimating a SPF for urban four-leg, signalized intersections. Since the case study exhibited signs of underdispersion, a Conway-Maxwell-Poisson Generalized Linear Model (GLM) was fitted to the data; then a quasi-Poisson model in the framework of Generalized Estim…

A generalized model for analyzing operational conditions at intersections in urban areas

2007

Modelling Photoionisations in Tautomeric DNA Nucleobase Derivatives 7H-Adenine and 7H-Guanine: Ultrafast Decay and Photostability

2021

The study of radiation effects in DNA is a multidisciplinary endeavour, connecting the physical, chemical and biological sciences. Despite being mostly filtered by the ozone layer, sunlight radiation is still expected to (photo)ionise DNA in sizeable yields, triggering an electron removal process and the formation of potentially reactive cationic species. In this manuscript, photoionisation decay channels of important DNA tautomeric derivatives, 7H-adenine and 7H-guanine, are characterised with accurate CASSCF/XMS-CASPT2 theoretical methods. These simulation techniques place the onset of ionisation for 7H-adenine and 7H-guanine on average at 8.98 and 8.43 eV, in line with recorded experimen…

Relationships between pollutant emissions from vehicles and levels of concentrations: a phenomenological approach

2005

The level of air quality in urban centres is affected by emission of several pollutants, mainly coming from the vehicles flowing in their road networks. This is a well known phenomenon that influences the quality of life of people. Despite the deep concern of researchers and technicians, we are far from a total understanding of this phenomenon. On the contrary, the availability of reliable forecasting models would constitute an important tool for administrators in order of assessing suitable actions concerning the transportation policies, public as well private. As matter of fact, the definition of a physical model requires the knowledge of many parameters, involving the running fleet, the …

Signalling Three-Way Intersections: Is Redundancy Better Than Only Mandatory or Prohibitory Signs?

2021

This work was supported by the Spanish Government, Ministry of Economy and Competitiveness (PGC2018-095868-B-I00).

Handling Underdispersion in Calibrating Safety Performance Function at Urban, Four-Leg, Signalized Intersections

2011

Poisson basic assumption of equidispersion is often too much restrictive for crash count data; in fact this type of data has been found to often exhibit overdispersion. Underdispersion has been less commonly observed, and this is the reason why it has been less convenient to model directly than overdispersion. Overdispersion and underdispersion are not the only issues that can be a potential source of error in specifying statistical models and that can lead to biased crash-frequency predictions; these issues can derive from data properties (temporal and spatial correlation, time-varying explanatory variables, etc.) or from methodological approach (omitted variables, functional form selectio…