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This is the best car in the garage.

We use articles like "the" and "a" before nouns, like "car". The word "best" is an adjective, and adjectives do not take articles by themselves. Because the noun "car" is modified by the superlative adjective "best", and because this makes the noun "car" definite in this context, we use "the".

It is best not to do something. Here, we have the adjective "best", but this adjective is attached to no noun.

The adjective "best" is used in a copular construction with the dummy pronoun "it". This pronoun does not refer to any object. There's no noun that we can attach "the" to here.