Fragmentation, structure, and energetics of small sodium formate clusters

Evidence for strong influence of entropic effects Dedicated to the memory of Detlef Schröder, an excellent scientist, mentor, colleague, and friend.

Ágnes Révész, T. Rokob, Gábor Maász, L. Márk, Helga Hevér, L. Drahos, K. Vékey

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The behavior of small cationic sodium formate clusters [NaOOCH] nNa+ was studied using a combination of experimental and theoretical approaches. Energy-dependent tandem mass spectra were measured using a triple quadrupole and an ion trap type instrument, while structure and energetics were obtained from density functional theory calculations. Analysis of the relative abundances and fragmentation patterns indicate the existence of certain unstable cluster sizes, like the tetramer [NaOOCH]4Na +. This observation is in contrast to alkali halides, where this species has enhanced stability. Surprisingly, this 'anti-magic' sodium formate cluster is shown to be compact, energetically low-lying by quantum chemical calculations. The apparent contradiction can be explained by taking into account entropy effects as calculated dissociation Gibbs free energy values show remarkably improved agreement with experimental trends. Fragmentation of these clusters is a good example of reactions that are predominantly directed by entropy and not by energy constraints.

Original languageEnglish
Pages (from-to)292-302
Number of pages11
JournalInternational Journal of Mass Spectrometry
Volume354-355
DOIs
Publication statusPublished - 2013

Fingerprint

formic acid
formates
fragmentation
Entropy
Sodium
sodium
Data storage equipment
Alkali halides
Gibbs free energy
Density functional theory
Ions
entropy
alkali halides
mass spectra
quadrupoles
dissociation
density functional theory
trends
energy

Keywords

  • Cluster stability
  • Entropy
  • Magic number
  • Quantum chemistry
  • Sodium formate
  • Tandem mass spectrometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Instrumentation

Cite this

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title = "Fragmentation, structure, and energetics of small sodium formate clusters: Evidence for strong influence of entropic effects Dedicated to the memory of Detlef Schr{\"o}der, an excellent scientist, mentor, colleague, and friend.",
abstract = "The behavior of small cationic sodium formate clusters [NaOOCH] nNa+ was studied using a combination of experimental and theoretical approaches. Energy-dependent tandem mass spectra were measured using a triple quadrupole and an ion trap type instrument, while structure and energetics were obtained from density functional theory calculations. Analysis of the relative abundances and fragmentation patterns indicate the existence of certain unstable cluster sizes, like the tetramer [NaOOCH]4Na +. This observation is in contrast to alkali halides, where this species has enhanced stability. Surprisingly, this 'anti-magic' sodium formate cluster is shown to be compact, energetically low-lying by quantum chemical calculations. The apparent contradiction can be explained by taking into account entropy effects as calculated dissociation Gibbs free energy values show remarkably improved agreement with experimental trends. Fragmentation of these clusters is a good example of reactions that are predominantly directed by entropy and not by energy constraints.",
keywords = "Cluster stability, Entropy, Magic number, Quantum chemistry, Sodium formate, Tandem mass spectrometry",
author = "{\'A}gnes R{\'e}v{\'e}sz and T. Rokob and G{\'a}bor Ma{\'a}sz and L. M{\'a}rk and Helga Hev{\'e}r and L. Drahos and K. V{\'e}key",
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T2 - Evidence for strong influence of entropic effects Dedicated to the memory of Detlef Schröder, an excellent scientist, mentor, colleague, and friend.

AU - Révész, Ágnes

AU - Rokob, T.

AU - Maász, Gábor

AU - Márk, L.

AU - Hevér, Helga

AU - Drahos, L.

AU - Vékey, K.

PY - 2013

Y1 - 2013

N2 - The behavior of small cationic sodium formate clusters [NaOOCH] nNa+ was studied using a combination of experimental and theoretical approaches. Energy-dependent tandem mass spectra were measured using a triple quadrupole and an ion trap type instrument, while structure and energetics were obtained from density functional theory calculations. Analysis of the relative abundances and fragmentation patterns indicate the existence of certain unstable cluster sizes, like the tetramer [NaOOCH]4Na +. This observation is in contrast to alkali halides, where this species has enhanced stability. Surprisingly, this 'anti-magic' sodium formate cluster is shown to be compact, energetically low-lying by quantum chemical calculations. The apparent contradiction can be explained by taking into account entropy effects as calculated dissociation Gibbs free energy values show remarkably improved agreement with experimental trends. Fragmentation of these clusters is a good example of reactions that are predominantly directed by entropy and not by energy constraints.

AB - The behavior of small cationic sodium formate clusters [NaOOCH] nNa+ was studied using a combination of experimental and theoretical approaches. Energy-dependent tandem mass spectra were measured using a triple quadrupole and an ion trap type instrument, while structure and energetics were obtained from density functional theory calculations. Analysis of the relative abundances and fragmentation patterns indicate the existence of certain unstable cluster sizes, like the tetramer [NaOOCH]4Na +. This observation is in contrast to alkali halides, where this species has enhanced stability. Surprisingly, this 'anti-magic' sodium formate cluster is shown to be compact, energetically low-lying by quantum chemical calculations. The apparent contradiction can be explained by taking into account entropy effects as calculated dissociation Gibbs free energy values show remarkably improved agreement with experimental trends. Fragmentation of these clusters is a good example of reactions that are predominantly directed by entropy and not by energy constraints.

KW - Cluster stability

KW - Entropy

KW - Magic number

KW - Quantum chemistry

KW - Sodium formate

KW - Tandem mass spectrometry

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