Gold chloride cluster anions grow as zigzag chains

LDI-MS detects Au_nCl_{n+3}– anions whose lowest isomers are zigzag chains starting from AuCl4–, growing exergonically by about 41–44 kcal mol–1.

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How were Au_nCl_{n+3}– ions observed?

LDI-TOF mass spectrometry of HAuCl4 (N2 laser, no matrix).

Which anion is most intense?

AuCl4–, not seen in the authors’ previous work.

What motif do the lowest Au_nCl_{n+3}– isomers share?

A zigzag skeleton starting from an AuCl4– unit.

What DFT level was used?

TPSSh with ECP60MDF on Au and aug-cc-pVTZ on Cl.

Is pathway R1 downhill?

Yes, ΔE −41 to −44 kcal mol–1 per growth step.

Where does larger-n binding energy settle?

About −41 kcal mol–1 for n > 6 on both R1 and R1′.

Are there Au–Au bonds in the lowest Au2Cl5– isomers?

Au···Au > 3.32 Å, so no aurophilic interaction there.

What are Au(I)–Au(I) distances for n = 3–7?

2.92 Å, slightly shorter than in Au_nCl_{n+1}–.

How much higher are internal-Au(III) zigzag isomers?

About 5–7 kcal mol–1 above the terminal-Au(III) lowest isomers.

Laser used on the Voyager instrument?

UV nitrogen laser, 337 nm, 3 ns pulses, 20 Hz.

HAuCl4 concentration on the target?

2.5 mg/mL, twice less sample than prior work.