Ionic Hydrogen Bonding Vibration in OH⁻(H₂O)_2-4

Abstract

Focusing on the OH⁻(H₂O)_2–4 clusters, we have theoretically studied the strongly red shifted ionic hydrogen bond (IHB) OH stretching vibration of water molecules directly bound to the hydroxide. Our calculations show that a systematic blue shift of the IHB OH peak is observed with the increase in the number of water molecules in the first solvation shell. Furthermore, we showed that the vibrational signature of the four coordinated hydroxide for OH⁻(H₂O)₄ will be observed in the 2800–3200 cm⁻¹ range.

Figures

Figure 1.

 Schematics of OH⁻(H₂O)₄ (a) isomer I, and (b) isomer II. The OH vibrations that were explicitly coupled in the vibrational calculation are represented with color coded arrows.

Figure 2.

 The top view schematic diagram for the four IHB vibrations for isomer II OH⁻(H₂O)_4.

Figure 3.

 The theoretical and experimental vibrational spectra of (a) OH⁻(H₂O)₂, (b) OH⁻(H₂O)₃, and (c) OH⁻(H₂O)₄. The experimental spectra of Ar-tagged predissociaiton spectroscopy [15] are given in solid red lines and flipped for visual clarity. The theoretical results are given in solid black lines, while contributions from different isomers or conformers are given in dotted blue/green/pink lines. We define conformers as different structural isomers which can be obtained by simple rotations around a bond, while we use the term isomer if bonds must be broken to connect those two structural isomers.

Tables

Table 1.  Peak position in cm⁻¹ and absorption intensity, in km mol⁻¹, for OH⁻(H₂O)₄ isomer I were calculated using B3LYP/6-31+G (d,p).

Assignment	Peak position	Intensity
IHB OH (antisymmetric combination of two DA waters in the side)	2028	2471
IHB OH (symmetric combination of two DA waters in the side)	2233	1230
IHB OH (central DD water)	3112	826
Second solvation (symmetric)	3345	340
Second solvation (antisymmetric)	3378	180
Free OH (symmetric combination of two DA waters in the side)	3705	7
Free OH (antisymmetric combination of two DA waters in the side)	3705	8
OH−	3715	2

Table 2.  Peak position in cm⁻¹ and absorption intensity, in km mol⁻¹, for OH⁻(H₂O)₄ isomer II were calculated using B3LYP/6-31+G (d,p).

Assignment	Peak position	Intensity
IHB OH (B symmetry combination of four waters)	2875	0
IHB OH (E symmetry combination of four waters)	2893	1587
IHB OH (E symmetry combination of four waters)	2893	1587
IHB OH (A symmetry combination of four waters)	3102	1047
Free OH (A symmetry combination of four waters)	3669	22
Free OH (E symmetry combination of four waters)	3672	45
Free OH (E symmetry combination of four waters)	3672	45
Free OH (B symmetry combination of four waters)	3674	0
OH−	3711	0

Table 3.  Zero point corrected binding energy, in kcal mol⁻¹, of a water molecule for OH⁻(H₂O)_n → OH⁻(H₂O)_n-1+H₂O calculated using B3LYP/6-31+G (d,p), and QCISD (T)/6-311++G (3df,3pd). The QCISD (T) energies are from our previous publication [23].

OH−(H2O)n	B3LYP	QCISD (T)
OH−(H2O)2	−20.13	−18.54
OH−(H2O)3	−17.09	−13.50
OH−(H2O)4	−11.90	−9.72

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