Ateneo - UPO

Il corso presenta approfondimenti e applicazioni pratiche, tramite esercizi numerici e formali, delle principali tecniche di modellizzazione teorica e computazionale in Chimica. Verranno trattati calcoli ab initio, principalmente DFT, post-Hartree Fock e multireference, e classici, basati su campi di forza applicati a Dinamiche Molecolari e simulazioni Monte Carlo.

Christopher J. Cramer, Essentials of Computational Chemistry: Theories and Models, 2nd Edition, John Wiley & Sons, 2004.Foresman, J. B., & Frisch, Æ. (2015). Exploring Chemistry with Electronic Structure Methods (3rd ed.). Gaussian, Inc. Ashcroft, N. W., & Mermin, N. D. (1976). Solid State Physics (1st ed.). Saunders College Publishing. Materiale fornito dal docente

Acquisire competenze pratiche e applicative nella modellizzazione quantistica e classica dei sistemi chimici: molecole, sistemi soluto/solvente, solidi porosi, superfici derivatizzate.
Apprendere i fondamenti delle principali tecniche di simulazione e modellizzazione usate nella chimica teorica.

Conoscenza della meccanica quantistica (al livello fornito dagli insegnamenti di Chimica Fisica della Laurea triennale in Chimica).
Molto utili, per quanto non indispensabili, i contenuti dell'insegnamento di Chimica teorica erogato nel corso magistrale in Scienze Chimiche, anche frequentato in contemporanea.

Lezioni frontali in aula.
Esercitazioni informatiche nelle postazioni del Dipartimento.

Gli esercizi numerici vengono eseguiti al calcolatore in ambiente Unix.Introduzione pratica ai sistemi operativi e all'uso del terminale verrano forniti all'inizio del corso

Esame orale.

Fortran Programming for Scientific Computing:

* Introduction to scientific programming and the concept of an algorithm.
* Translation of a scientific problem into input, operations, and output.
* Programming languages and the role of Fortran in scientific computing.
* Installation and use of the GFortran compiler.
* General structure of a Fortran program.
* Declaration of variables and main data types.
* Explicit typing and use of `implicit none`.
* Arithmetic operators, expressions, and type conversions.
* Numerical precision and use of double precision.
* Input and output operations with `read`, `print`, and `write`.
* Formatting of integers, real numbers, strings, and scientific notation.
* Reading from and writing to external files.
* Management of input/output errors using `iostat`.
* Conditional structures `if–then–else`.
* Iterative loops `do` and `do while`.
* One-dimensional and multidimensional arrays.
* Dynamic memory allocation and deallocation.
* Vector operations and intrinsic array functions.
* Implementation of simple physicochemical models.
* Calculation of the average kinetic energy of an ideal gas.
* Modular programming using functions and subroutines.
* Argument passing and `intent` attributes.
* Use of Fortran modules to organize code.
* Quantum-mechanical application to the particle in a box.
* Numerical representation and manipulation of matrices.
* Calculation of eigenvalues and eigenvectors.
* Use of the BLAS and LAPACK numerical libraries.
* Diagonalization of symmetric matrices using `DSYEV`.
* Verification of diagonalization through matrix transformations.
* Jacobi iterative method for diagonalization.
* Numerical integration using the trapezoidal rule.
* String manipulation and substring searching.
* Automatic extraction of data from scientific program output files.
* Extraction of free energies from Gaussian output files.

DFT:

* Geometry optimizations.
* Simulation of vibrational spectra (IR).
* Simulation of UV/Vis spectra using TDDFT.
* Simulation of circular dichroism spectra using TDDFT.
* Simulation of chemical reactions using the IRC approach.
* Calculation of relative energies and Boltzmann populations.
* Introduction to potential energy surfaces.
* Minima, transition states, and saddle points.
* Optimization of transition states with Gaussian.
* TS, QST2, and QST3 methods.
* Analysis of vibrational and imaginary frequencies.
* Qualitative verification of the normal mode associated with the transition state.
* Calculation and interpretation of the Intrinsic Reaction Coordinate.
* Analysis of energy profiles along the reaction path.
* Comparison of different reaction channels and transition states.
* Interpretation of stereochemical selectivity.
* Distinction between kinetic and thermodynamic control.
* Relationship among free energy, equilibrium constant, and rate constant.
* Application of the Eyring equation to the prediction of selectivity.

Post-Hartree–Fock Methods:

* Calculation of multireference electronic structures.
* Simulation of optical spectra using CASSCF.

Classical Methods, Introduction to Solid-State Systems, and Simulations with LCAO and Plane-Wave Codes:

* Molecular dynamics.
* Free-energy calculations using thermodynamic integration.
* Simulation of adsorption processes using Monte Carlo techniques.

Capacità di progettare e eseguire in autonomia simulazioni di sistemi chimici con diverse tecniche teoriche e computazionali.
Capacità di modellizzare diversi problemi chimici, e delle tecniche di simulazione più adeguate.