One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays : сборник научных трудов

Тип публикации: статья из журнала

Год издания: 2018

Идентификатор DOI: 10.1103/PhysRevA.97.053410

Аннотация: The concept of the potential-energy surface (PES) and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to (near) degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close-lying vibrational levels. We show here that resonant inelastic x-ray scattering (RIXS) constitutes an ideal probe for revealing one-dimensional cuts through the ground-state PES of molecular systems, even far away from the equilibrium geometry, where the independent-mode picture is broken. We strictly link the center of gravity of close-lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one-dimensional Hamiltonian along the propagation coordinate of the core-excited wave packet. This concept, combined with directional and site selectivity of the core-excited states, allows us to experimentally extract cuts through the ground-state PES along three complementary directions for the showcase H2O molecule.

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Издание

Журнал: PHYSICAL REVIEW A

Выпуск журнала: Vol. 97, Is. 5

Номера страниц: 53410

ISSN журнала: 24699926

Место издания: COLLEGE PK

Издатель: AMER PHYSICAL SOC

Авторы

  • Eckert Sebastian (Univ Potsdam, Inst Phys & Astron, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany; Helmholtz Zentrum Berlin Mat & Energie, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany)
  • da Cruz Vinicius Vaz (Royal Inst Technol, Theoret Chem & Biol, S-10691 Stockholm, Sweden)
  • Gel'mukhanov Faris (Royal Inst Technol, Theoret Chem & Biol, S-10691 Stockholm, Sweden; Siberian Fed Univ, Inst Nanotechnol Spect & Quantum Chem, Krasnoyarsk 660041, Russia)
  • Ertan Emelie (Stockholm Univ, AlbaNova Univ Ctr, Dept Phys, S-10691 Stockholm, Sweden)
  • Ignatova Nina (Royal Inst Technol, Theoret Chem & Biol, S-10691 Stockholm, Sweden; Siberian Fed Univ, Inst Nanotechnol Spect & Quantum Chem, Krasnoyarsk 660041, Russia)
  • Polyutov Sergey (Siberian Fed Univ, Inst Nanotechnol Spect & Quantum Chem, Krasnoyarsk 660041, Russia)
  • Couto Rafael C. (Royal Inst Technol, Theoret Chem & Biol, S-10691 Stockholm, Sweden)
  • Fondell Mattis (Helmholtz Zentrum Berlin Mat & Energie, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany)
  • Dantz Marcus (PSI, Res Dept Synchrotron Radiat & Nanotechnol, CH-5232 Villigen, Switzerland)
  • Kennedy Brian (Helmholtz Zentrum Berlin Mat & Energie, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany)
  • Schmitt Thorsten (PSI, Res Dept Synchrotron Radiat & Nanotechnol, CH-5232 Villigen, Switzerland)
  • Pietzsch Annette (Helmholtz Zentrum Berlin Mat & Energie, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany)
  • Odelius Michael (Stockholm Univ, AlbaNova Univ Ctr, Dept Phys, S-10691 Stockholm, Sweden)
  • Foehlisch Alexander (Univ Potsdam, Inst Phys & Astron, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany; Helmholtz Zentrum Berlin Mat & Energie, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany)

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