Bruno Martínez Haya
  Profesor Titular in Physical Chemistry 
  Department  of Physical, Chemical and Natural Systems

  Universidad Pablo de Olavide, 41013 Seville, Spain.
  tel: +34-954-977562, fax: +34-954-349814
  email: bmarhayupo.es

  Lines of Research (click on them or see below for details):

  - Laser spectroscopy and Mass Spectrometry of Biomolecules and Polymers
  - Dynamics of Elementary and Photoinitiated Reactions

  - Statistical Mechanics of Simple Fluids

  Ana Rodríguez Hortal
   Ph.D. research fellow 
   email: arodhorupo.es

  Paola Hurtado Castillo
   Ph.D. research fellow 
   email: pmhurcasupo.es

 Laser Spectroscopy and Mass Spectrometry of Biomolecules and Polymers


Imagen del dispositivo MALDIOur laboratory is equipped with a Laser Spectroscopy and Mass Spectrometry apparatus (MALDI-TOF, REMPI-TOF) designed for versatile performance. Laser desorption and ionisation of sample molecules can be performed at the ion source. Alternatively, the sample molecules can be prepared in a supersonic expansion at a low terminal temperature by means of a pulsed beam source. A Nd:YAG-pumped Dye laser system provides tunable pulsed laser radiation in the range 220-480nm for MALDI at specific wavelengths and spectroscopy experiments employing Resonance Enhanced Multiphoton Ionisation (REMPI).

We have been investigating different families of molecules, mainly biomolecules (peptides, oligosaccharies), synthetic polymers, triazinic pesticides and asphaltene extracts from crude oils. We are testing novel MALDI sample preparation methods, based on solvent-free approaches, as well as on ionic liquid matrices. By combining MALDI and molecular beam ion spectoscopy we intend to study non-covalent aggregation and molecular recognition processes on model systems.

We collaborate in this field with Luis Bañares (Universidad Complutense de Madrid), Anna Giardini (University of Rome), John P. Simons (University of Oxford), Oliver C. Mullins (Schlumberger-Doll Research, USA), and others. 

Selected publications in the field of Laser spectroscopy and mass spectrometry:

"Fragmentation and gas phase aggregation processes in the laser desorption ionization of chlorodiaminotriazines" P. Hurtado, A.R. Hortal, M. Cruz-Guzmán, B. Martínez-Haya, European Journal of Mass Spectrometry (2007) in press.

"MALDI detection of carbonaceous compounds in ionic liquid matrices" P. Hurtado, A.R. Hortal, B. Martínez-Haya, Rapid Communications in Mass Spectrometry 21 (2007) 3161-3164.

"Molecular-weight distributions of coal and petroleum asphaltenes from laser desorption/ionization experiments" A.R.Hortal, P.Hurtado, B. Martínez-Haya, O.C. Mullins, Energy & Fuels 21 (2007) 2863-2868.

"Laser desorption/ionization determination of molecular weight distributions of polyaromatic carbonaceous compounds and their aggregates"  B. Martínez-Haya, A.R. Hortal, P. Hurtado, M. Lobato, J.M. Pedrosa, Journal of Mass Spectrometry, 42 (2007) 701-713.

"Characterization and Langmuir film properties of asphaltenes extracted from Arabian light crude oil" M. Lobato, J.M. Pedrosa, A.R. Hortal, B. Martínez-Haya, S. Lago,  Colloid & Surfaces A, 298 (2007) 72-79.

"On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments" A.R. Hortal, B. Martínez-Haya, M. Lobato, J.M. Pedrosa, S. Lago,  Journal of Mass Spectrometry, 41 (2006) 960-968.

  Research in the field of Elementary and Photoinitated Reaction Dynamics

- High resolution crossed molecular beam investigation of the elementary reaction F + H2. Determination of absolute differential state-to-state cross sections for the HF products. Dependence on initial rotation of the hydrogen molecule. This was my Ph.D. project (1992-96), supervised by Prof. J.P. Toennies at the Max-Planck Institut für Strömungsforschung (Max-Planck Institute for Fluid Dynamics) in the city of Göttingen (Germany). 

 

- Laser Multiphoton Ionization (REMPI-TOF and velocity-map ion-imaging) study of the photodissociation of organosulfides and other methylated molecules (e.g., ICH3, CH3SCH3, CH3S2CH3), and the rotational relaxation of molecules (N2, CO, H2)  in supersonic expansions. Experiments performed during my postdoctoral stay (1997-1999) in the lab of Javier Aoiz at the Physical Chemistry Department of the Universidad Complutense de Madrid, and as Royal Society visiting scientist in the lab of Mark Brouard (Oxford, England).  

 

- Quantum and quasiclassical theoretical Reaction Dynamics investigations. Determination of scalar observables, such as state-to-state differential and integral cross sections or rate constants, and vectorial properties (polarization dependent cross sections) characterising the estereodynamics of the reaction. The chemical systems investigated are three-atom and four-atom bechmark gas-phase reactions. These are a few examples:   H+H2 , F+H2 , O+H2 , and, more recently, H+O2 and Cl+O3.

Selected publications in the field of Elementary Reaction Dynamics:

"Quasiclassical determination of reaction probabilities as a function of the total angular momentum" F.J. Aoiz, V.Sáez-Rábanos, B.Martínez-Haya, T.González-Lezana, Journal Chemical Physics, 123 (2005)  094101.

"Photodissociation and Multiphoton Dissociative Ionisation Processes in CH3S2CH3 at 193 nm Studied using Velocity-map Imaging" B. Martínez-Haya, M.J. Bass, M. Brouard, C. Vallance, I. Torres, J. Barr. Journal of Chemical Physics, 120 (2004)  p.11042

"Angular momentum alignment of Cl(2P3/2) in the 308 nm photolysis of Cl2 determined using Fourier moment velocity-map imaging" M.J. Bass,  M. Brouard, A.P. Clark, C. Vallance and B. Martínez-Haya, Physical Chemistry Chemical Physics, 5 (2003) p. 856

"The photodissociation of CH3SCH3 and CD3SCD3 at 220--231nm investigated by velocity map ion imaging" B. Martínez-Haya, P. Quintana, L. Bañares , P. Samartzis, D.J. Smith,  T.N. Kitsopoulos, Journal of Chemical Physics, 114 (2001)  p. 4450.

"The Low Temperature Rotational Relaxation of N2 studied with Resonance Enhanced Multiphoton Ionization" F.J. Aoiz, T. Díez Rojo, V.J. Herrero, B. Martínez-Haya, M. Menéndez, P. Quintana, L. Ramonat, I. Tanarro and E. Verdasco, Journal of Physical Chemistry, 103 (1999) p.823

"Rotational State Resolved Differential Cross Sections for the Reaction F+D2>DF+D at Collision Energies 140-240 meV" M.Faubel, B.Martínez-Haya, L.Y. Rusin, U. Tappe, J.P.Toennies, F.J.Aoiz and L.Bañares. Journal of Physical Chemistry, 102 (1998) p.8695.

"State-to-state differential cross sections for the reaction F+D2 at 90meV: a crossed molecular beam experiment and a quantum mechanical study" M. Baer, M. Faubel, B. Martínez-Haya, L.Y. Rusin, U. Tappe y J.P. Toennies. Journal of Chemichal Physics, 108 (1998) p.9694

"Elastic and Rotationally Inelastic Scattering of Fluorine Atoms by Deuterium Molecules at 112meV Collision Energy" M. Ayabakan, M. Faubel, B. Martínez-Haya, L.Y. Rusin, M.B. Sevryuk, U. Tappe, J.P. Toennies. Chemical Physics 229 (1998) 21

"Quantum mechanical and Quasi-classical Simulations of Molecular Beam Experiments for the F+H2>HF+H Reaction on two ab initio potential energy surfaces" J.F. Castillo, B. Hartke, H.J. Werner, F.J. Aoiz, L. Bañares and B. Martínez-Haya. Journal of Chemical Physics, 109 (1998) 7224.

"Experimental Absolute Cross Sections for the Reaction F+D2 at Collision Energies 90-240meV" M. Faubel, B.Martínez-Haya, L.Y.Rusin, U.Tappe, J.P.Toennies. Journal of Physical Chemistry, 101 (1997) 6415

"The H+D2 Reaction in the Vicinity of the Conical Intersection" E. Wrede, L. Schnieder, K.H. Welge, F.J. Aoiz, L. Bañares, V.J. Herrero, B. Martínez-Haya and V. Sáez Rábanos Journal of Chemical Physics, 106 (1997) 7862

My research in Statistical Mechanics of Simple Fluids
 

Statistical Mechanics (Monte Carlo and Molecular Dynamics computer simulations, Integral Equation techniques)  investigation of simple rigid models of anisotropic molecular fluids with different dispersive and electrostatic intermolecular interactions. In collaboration with Alejandro Cuetos (currently postdoc at the Debye Institute, Utrecht), Carmen Gordillo and  Juan Antonio Anta(Universidad Pablo de Olavide), Jose Manuel Romero and Luis Rull (Universidad de Sevilla). 

We have been looking into the Liquid Crystal phases  (isotropic, nematic, smectic, hexatic) of fluids of prolate and oblate molecules dressed with different types of Kihara-type interaction potentials and in binary mixtures with spherical molecules. We have proposed a novel interaction model for these molecular fluids featuring an orientation-dependence of the pair interaction energy.  The model combines distinct properties of the well known Kihara and Gay-Berne pair potentials.

Selected publications in the field of Statistical Mechanics of Simple Fluids:

"Stability of Nematic and Smectic phases in rod-like mesogens with orientation-dependent attractive interactions" B. Martínez-Haya, A. Cuetos, Journal of Physical Chemistry B, 111 (2007) 8150-8157

"Use of Parsons-Lee and Onsager theories to predict nematic and demixing behavior in binary mixtures of hard rods and spheres" A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Physical Review E, 75 (2007) 061701 1-12

"Effect of Macromolecular Crowding on the conformation of confined Chain Polymers" B. Martínez-Haya and M.C. Gordillo, Macromolecular Theory and Simulations, 14 (2005) p. 421

"Parsons-Lee and Monte Carlo study of soft repulsive nematogens"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Journal of Physical Chemistry B,  109 (2005) p.13729

"A Novel Orientation-dependent Potential Model for Prolate Mesogens"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Journal of Chemical Physics,  122 (2005)  024908

"Crowding Effects in Binary Mixtures of Rod-like and Spherical Particles"  S. Lago, A. Cuetos,  B. Martínez-Haya, L.F. Rull. Journal of Molecular Recognition, 17 (2004) p.417.

"Liquid Crystal Behavior of the Kihara Fluid"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull, Physical Review E, 68 (2003) 0011704.

"Monte Carlo Study of Liquid Crystal Phases of Hard and Soft Spherocylinders"  A. Cuetos,  B. Martínez-Haya, L.F. Rull, S. Lago. Journal of Chemical Physics, 117 (2002) p.2034. Erratum, ibid. 117 (2002) p.11405.

"Gibbs-Ensemble Simulation of the Vapor-liquid Equilibrium of Square Well Spherocylinders" B. Martínez-Haya, L.F. Rull, A. Cuetos, S. Lago. Molecular Physics 99  (2001) p.509

"Analytical Solution to a Non-separable Interaction Model for a One-dimensional Fluid of Anisotropic Molecules near a Hard Wall" B. Martínez-Haya, J.M. Pastor, J.A. Cuesta. Physical Review E, 59 (1999) 1957