The Martian Way: a collection by Isaac Asimov. If I wanted to hand someone one book to hook them on Asimov, I think it would be this one or Nine Tomorrows - both contain short work that is some of his very best.

The Martian Way
Youth
The Deep
Sucker Bait

These appeared in 1952/1954 - in Galaxy, Space SF, and Astounding.