PMID- 37406194
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230720
IS  - 1520-5215 (Electronic)
IS  - 1089-5639 (Linking)
VI  - 127
IP  - 28
DP  - 2023 Jul 20
TI  - Quantifying the Impact of Halogenation on Intermolecular Interactions and Binding 
      Modes of Aromatic Molecules.
PG  - 5823-5832
LID - 10.1021/acs.jpca.3c02291 [doi]
AB  - Halogenation of aromatic molecules is frequently used to modulate intermolecular 
      interactions with ramifications for optoelectronic and mechanical properties. In 
      this work, we accurately quantify and understand the nature of intermolecular 
      interactions in perhalogenated benzene (PHB) clusters. Using benchmark binding 
      energies from the fixed-node diffusion Monte Carlo (FN-DMC) method, we show that 
      generalized Kohn-Sham semicanonical projected random phase approximation 
      (GKS-spRPA) plus approximate exchange kernel (AKX) provides reliable interaction 
      energies with mean absolute error (MAE) of 0.23 kcal/mol. Using the GKS-spRPA+AXK 
      method, we quantify the interaction energies of several binding modes of PHB 
      clusters ((C(6)X(6))(n); X = F, Cl, Br, I; n = 2, 3). For a given binding mode, 
      the interaction energies increase 3-4 times from X = F to X = I; the X-X binding 
      modes have energies in the range of 2-4 kcal/mol, while the pi-pi binding mode has 
      interaction energies in the range of 4-12 kcal/mol. SAPT-DFT-based energy 
      decomposition analysis is then used to show that the equilibrium geometries are 
      dictated primarily by the dispersion and exchange interactions. Finally, we test 
      the accuracy of several dispersion-corrected density functional approximations 
      and show that only the r2SCAN-D4 method has a low MAE and correct long-range 
      behavior, which makes it suitable for large-scale simulations and for developing 
      structure-function relationships of halogenated aromatic systems.
FAU - Tyagi, Ritaj
AU  - Tyagi R
AUID- ORCID: 0000-0003-2424-4627
AD  - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi 
      Bhabha Road, Colaba, Mumbai 400005, India.
FAU - Zen, Andrea
AU  - Zen A
AUID- ORCID: 0000-0002-7648-4078
AD  - Dipartimento di Fisica Ettore Pancini, Universita di Napoli Federico II, Monte S. 
      Angelo, I-80126 Napoli, Italy.
FAU - Voora, Vamsee K
AU  - Voora VK
AUID- ORCID: 0000-0002-4887-0609
AD  - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi 
      Bhabha Road, Colaba, Mumbai 400005, India.
LA  - eng
PT  - Journal Article
DEP - 20230705
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
SB  - IM
EDAT- 2023/07/05 19:12
MHDA- 2023/07/05 19:13
CRDT- 2023/07/05 15:33
PHST- 2023/07/05 19:13 [medline]
PHST- 2023/07/05 19:12 [pubmed]
PHST- 2023/07/05 15:33 [entrez]
AID - 10.1021/acs.jpca.3c02291 [doi]
PST - ppublish
SO  - J Phys Chem A. 2023 Jul 20;127(28):5823-5832. doi: 10.1021/acs.jpca.3c02291. Epub 
      2023 Jul 5.